CN111229201B - Mo-based catalyst taking scheelite oxide as precursor, and preparation method and application thereof - Google Patents

Mo-based catalyst taking scheelite oxide as precursor, and preparation method and application thereof Download PDF

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CN111229201B
CN111229201B CN202010079048.1A CN202010079048A CN111229201B CN 111229201 B CN111229201 B CN 111229201B CN 202010079048 A CN202010079048 A CN 202010079048A CN 111229201 B CN111229201 B CN 111229201B
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scheelite
precursor
oxide
magnesium
based catalyst
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CN111229201A (en
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张立红
王佳萌
韩明迅
葛蒙
李响响
鲁逸人
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Tianjin University
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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
    • B01J23/16—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • 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
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a Mo-based catalyst taking scheelite oxide as a precursor, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Dissolving ammonium molybdate and a magnesium-containing compound in water, and adding citric acid for dissolution, wherein the molar ratio of the citric acid to the ammonium molybdate to the magnesium-containing compound is 1.2:0.5:0.5; (2) Adding silicon dioxide into the aqueous solution obtained in the step (1), wherein the molar ratio of the silicon dioxide to the magnesium-containing compound is (7.17-27.63): 1, standing for 12-24 hours, drying and roasting to obtain the Mo-based catalyst MgMoO taking scheelite oxide as precursor 4 /SiO 2 . The Mo-based catalyst taking scheelite oxide as a precursor is used for the direct dehydrogenation reaction of isobutane to prepare isobutene after different reduction conditions, and the conversion rate is still stable at 12-20% after the reaction time of 6 hours, so that the catalyst has good stability.

Description

Mo-based catalyst taking scheelite oxide as precursor, and preparation method and application thereof
Technical Field
The invention relates to a structural catalyst and a preparation method and application thereof, in particular to a Mo-based catalyst taking scheelite oxide as a precursor and a preparation method and application thereof.
Background
Isobutene is an important raw material for producing polybutene, methyl tertiary butyl ether, ethyl tertiary butyl ether and other substances, and along with the development of economy, the demand of the derivative products is rapidly increased, so that the demand of the market on the derivative products is driven, and the derivative products become current scarce resources. However, conventional methods for producing isobutene by steam cracking, fluid catalytic cracking units, etc. have failed to meet the current demand for isobutene. In recent years, the production process for producing isobutene by direct dehydrogenation of isobutane has attracted extensive attention from researchers, and provides an economic and effective production path.
The isobutane direct dehydrogenation catalysts currently used in industry are Pt-based catalysts and Cr-based catalysts. Although both the catalyst show better dehydrogenation reaction performance, the Pt-based catalyst has the problems of high production cost, easy sintering, serious carbon deposition and the like; the Cr-based catalyst has the problems of over-quick deactivation, environmental pollution and the like. Therefore, it is very necessary to develop a novel low-cost and environment-friendly isobutane dehydrogenation catalyst.
The Mo-based catalyst is used as a transition metal oxide capable of providing lattice oxygen, is relatively suitable in price and is non-toxic to the environment, and can be considered to be used in an isobutane dehydrogenation system. MoOx is dispersed on different carriers by Wangguo, and the direct dehydrogenation reaction performance of isobutane is systematically researched, and the experimental result shows that Mo/MgAl 2 O 4 The selectivity of the catalyst to isobutene can reach about 78%, and the conversion rate of isobutane is 45%. Zhao et al demonstrated that ordered mesoporous molybdenum aluminum catalysts with strong metal carrier interactions have better stability and coking resistance compared to disordered mesoporous molybdenum aluminum catalysts.
The current report about the use of Mo-based catalyst in the reaction of preparing isobutene by directly dehydrogenating isobutane is less, the activity is low and unstable, and the valence state of the active species is not clear.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a Mo-based catalyst which takes scheelite oxide as a precursor and is low in cost and stable in direct dehydrogenation of isobutane.
The second object of the present invention is to provide a method for preparing a Mo-based catalyst using scheelite type oxide as a precursor.
A third object of the present invention is to provide the use of a Mo-based catalyst with scheelite type oxide as a precursor.
The technical scheme of the invention is summarized as follows:
mo-based catalyst with scheelite oxide as precursor and with molecular formula of MgMoO 4 /SiO 2 。
The preparation method of the Mo-based catalyst taking scheelite oxide as a precursor comprises the following steps:
(1) Dissolving ammonium molybdate and a magnesium-containing compound in water, and adding citric acid for dissolution, wherein the molar ratio of the citric acid to the ammonium molybdate to the magnesium-containing compound is 1.2:0.5:0.5;
(2) Adding silicon dioxide into the aqueous solution obtained in the step (1), wherein the molar ratio of the silicon dioxide to the magnesium-containing compound is (7.17-27.63): 1, standing for 12-24 hours, drying and roasting to obtain the Mo-based catalyst MgMoO taking scheelite oxide as precursor 4 /SiO 2 。
The magnesium-containing compound is preferably: magnesium nitrate, magnesium chloride or magnesium acetate.
Preferably: the roasting temperature is 580-640 ℃, and the roasting time is 4-6 hours.
The application of the Mo-based catalyst taking scheelite oxide as a precursor in catalyzing isobutane to be directly dehydrogenated to generate isobutene.
The Mo-based catalyst taking scheelite oxide as a precursor is used for the direct dehydrogenation reaction of isobutane to prepare isobutene after different reduction conditions, and the conversion rate is still stable at 12-20% after the reaction time of 6 hours, so that the catalyst has good stability.
Drawings
Fig. 1 is an XRD pattern of a Mo-based catalyst of the present invention using scheelite type oxide as a precursor.
FIG. 2 is a graph showing the reactivity of the catalyst prepared in example 1, which was not reduced, was reduced for 2 hours and was reduced for 4 hours, and was used for the direct dehydrogenation of isobutane to prepare isobutene.
FIG. 3 is a graph showing the performance of the catalyst prepared in example 1 for direct dehydrogenation of isobutane to isobutene after reduction for 2 hours at different reduction temperatures.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Silica with a specific surface area of 348m 2 Per gram, average pore diameter of 10.7nm, pore volume of 1.0cm 3 By way of example,/g, other silica sizes may also be used in the present invention.
Example 1
The preparation method of the Mo-based catalyst taking scheelite oxide as a precursor comprises the following steps:
(1) Ammonium molybdate (0.5749 g,0.00325 mol) and magnesium nitrate (0.853 g,0.00325 mol) were dissolved in 3ml of distilled water, and citric acid (1.6424 g, 0.007882 mol) was added thereto,
(2) Adding silicon dioxide (1.4 g,0.0233 mol) (the mol ratio of the silicon dioxide to the magnesium nitrate is 7.17:1) into the aqueous solution obtained in the step (1), standing for 24 hours, drying at 120 ℃, and roasting at 600 ℃ for 5 hours to obtain a Mo-based catalyst MgMoO taking scheelite type oxide as a precursor 4 /SiO 2 The X-ray diffraction pattern XRD is shown in figure 1.
Example 2
The catalyst prepared in example 1 was charged into a fixed bed reactor, and mixed gas of isobutane and hydrogen was introduced without reduction in a molar ratio of 1:1 at a volume space velocity of 3h -1 And carrying out dehydrogenation reaction at the reaction temperature of 600 ℃ to obtain the isobutene.
The catalyst prepared in example 1 was charged into a fixed bed reactor, a hydrogen-nitrogen mixture gas (hydrogen-nitrogen volume ratio: 1:19) preheated to 100℃was introduced, and after reduction at 600℃for 2 hours, an isobutane-hydrogen mixture gas in a molar ratio of 1:1 was introduced, and the space velocity was 3 hours -1 And carrying out dehydrogenation reaction at the reaction temperature of 600 ℃ to obtain the isobutene.
The catalyst prepared in example 1 was charged into a fixed bed reactor,introducing hydrogen-nitrogen mixed gas (the volume ratio of hydrogen to nitrogen is 1:19) preheated to 100 ℃, reducing for 4 hours at 600 ℃, introducing isobutane and hydrogen mixed gas with the molar ratio of 1:1, and controlling the volume space velocity to be 3 hours -1 And carrying out dehydrogenation reaction at the reaction temperature of 600 ℃ to obtain the isobutene.
The catalyst is reduced under certain conditions before use, so that the catalyst contains active species with different valence states before being used for the reaction of preparing isobutene by directly dehydrogenating isobutane. The active species with different valence states is Mo 6+ 、Mo 4+ 、Mo 2+ 、Mo。
See fig. 2.
As can be seen from fig. 2, the catalyst prepared in this example had better performance after reduction than that without reduction, that is, the low valence Mo species was more favorable for dehydrogenation.
Example 3
The catalyst prepared in example 1 was charged into a fixed bed reactor, a hydrogen-nitrogen mixture gas (hydrogen-nitrogen volume ratio: 1:19) preheated to 100℃was introduced, and after reduction at 600℃and 650℃and 700℃for 2 hours, an isobutane-hydrogen mixture gas in a molar ratio of 1:1 was introduced, and the volume space velocity was 3 hours -1 And carrying out dehydrogenation reaction at the reaction temperature of 600 ℃ to obtain the isobutene. See fig. 3.
Example 4
The preparation method of the Mo-based catalyst taking scheelite oxide as a precursor comprises the following steps:
(1) Ammonium molybdate (0.5749 g,0.00325 mol) and magnesium chloride (0.6607 g,0.00325 mol) were dissolved in 3ml distilled water, and citric acid (1.6424 g,0.00782 mol) was added thereto,
(2) To the aqueous solution obtained in step (1), silica (5.3898 g,0.0898 mol) was added in a molar ratio of silica to magnesium chloride of 27.63:1, standing for 18 hours, drying at 120 ℃ and roasting at 580 ℃ for 6 hours to obtain the Mo-based catalyst MgMoO taking scheelite oxide as precursor 4 /SiO 2 。
Example 5
The preparation method of the Mo-based catalyst taking scheelite oxide as a precursor comprises the following steps:
(1) Ammonium molybdate (0.5749 g,0.00325 mol) and magnesium acetate (0.6968 g,0.00325 mol) were dissolved in 3ml distilled water, and citric acid (1.6424 g,0.00782 mol) was added thereto,
(2) To the aqueous solution obtained in step (1), silica (2.925 g,0.0487 mol) was added, the molar ratio of silica to magnesium acetate being 15:1, standing for 12 hours, drying at 120 ℃ and roasting at 640 ℃ for 4 hours to obtain the Mo-based catalyst MgMoO taking scheelite oxide as precursor 4 /SiO 2 。
The catalysts prepared in examples 2 and 3 had better performance after reduction than the non-reduced, low-valence Mo species, which was more favorable for dehydrogenation.

Claims (1)

1. The application of a Mo-based catalyst taking scheelite oxide as a precursor to catalyzing isobutane to be directly dehydrogenated to generate isobutene is characterized by comprising the following steps:
loading a Mo-based catalyst taking scheelite oxide as a precursor into a fixed bed reactor, and introducing hydrogen-nitrogen mixed gas preheated to 100 ℃, wherein the hydrogen-nitrogen volume ratio is 1:19, after reducing for 2 hours at 600, 650 or 700 ℃, or after reducing for 4 hours at 600 ℃, introducing mixed gas of isobutane and hydrogen with the mol ratio of 1:1, and controlling the volume space velocity to be 3 hours -1 Carrying out dehydrogenation reaction at the reaction temperature of 600 ℃ to obtain isobutene;
the molecular formula of the Mo-based catalyst taking scheelite oxide as a precursor is MgMoO 4 /SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The method comprises the following steps:
(1) Dissolving ammonium molybdate and a magnesium-containing compound in water, and adding citric acid for dissolution, wherein the molar ratio of the citric acid to the ammonium molybdate to the magnesium-containing compound is 1.2:0.5:0.5;
(2) Adding silicon dioxide into the aqueous solution obtained in the step (1), wherein the molar ratio of the silicon dioxide to the magnesium-containing compound is (7.17-27.63): 1, standing for 12-24 hours, drying and roasting to obtain the Mo-based catalyst MgMoO taking scheelite oxide as precursor 4 /SiO 2 ；
The magnesium-containing compound is magnesium nitrate, magnesium chloride or magnesium acetate;
the roasting temperature is 580-640 ℃, and the roasting time is 4-6 hours.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1473654A (en) * 2002-08-06 2004-02-11 中国科学院大连化学物理研究所 Composite oxide catalyst and its preparing method and use
CN103861597A (en) * 2012-12-18 2014-06-18 中国科学院大连化学物理研究所 Supported spinel compound and preparation and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1473654A (en) * 2002-08-06 2004-02-11 中国科学院大连化学物理研究所 Composite oxide catalyst and its preparing method and use
CN103861597A (en) * 2012-12-18 2014-06-18 中国科学院大连化学物理研究所 Supported spinel compound and preparation and application thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Production of biodiesel from waste cooking oil using MgMoO4-supported TiO2 as a heterogeneous catalyst;M. Karthikeyan等;《ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS》;20171115;第2053-2059页 *
V-Mo-Mg／SiO2负载型催化剂的制备及甲醇氧化制甲醛反应性能的研究;张轶等;《沈阳化工学院学报》;20080630;第116-118页 *
王国玮等.异丁烷催化脱氢反应中钼基催化剂载体效应的研究.《石油炼制与化工》.2014,第15-19页. *
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