CN114713253A - Method for preparing pure alpha-phase molybdenum carbide catalyst through one-step carbonization, catalyst and application - Google Patents
Method for preparing pure alpha-phase molybdenum carbide catalyst through one-step carbonization, catalyst and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 67
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000003763 carbonization Methods 0.000 title claims abstract description 45
- 239000010948 rhodium Substances 0.000 claims abstract description 56
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 54
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 46
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- YKJSOAKPHMIDLP-UHFFFAOYSA-J 2-ethylhexanoate;molybdenum(4+) Chemical compound [Mo+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O YKJSOAKPHMIDLP-UHFFFAOYSA-J 0.000 claims 1
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- 229940010552 ammonium molybdate Drugs 0.000 claims 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims 1
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- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 229910003182 MoCx Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 1
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- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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- -1 transition metal carbides Chemical class 0.000 description 1
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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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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- C01B32/949—Tungsten or molybdenum carbides
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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Abstract
The invention discloses a method for preparing a pure alpha-phase molybdenum carbide catalyst by one-step carbonization induced by noble metal rhodium and application thereof. The preparation method comprises the following steps: (1) preparing molybdenum trioxide powder by adopting a flame spraying method; (2) dipping molybdenum trioxide powder into a rhodium salt solution, and drying to obtain noble metal-loaded molybdenum trioxide; (3) carbonizing the sample obtained in the step (2) under a carbon source gas. According to the invention, the molybdenum trioxide nano particles are prepared by using a flame spraying method, the carbonization process of molybdenum trioxide can be obviously changed by using trace noble metal rhodium, alpha-phase molybdenum carbide with higher purity can be obtained by one-step carbonization, and the ammoniation process with high pollution is omitted. The invention also discloses a rhodium-loaded alpha-phase molybdenum carbide catalyst and application thereof in a water-vapor transformation reaction, and the result shows that the molybdenum carbide catalyst prepared by the method has higher activity and stability.
Description
Technical Field
The invention relates to a molybdenum carbide catalyst which is formed by converting molybdenum oxide into rhodium-loaded molybdenum carbide through one-step embodiment 1 after loading noble metal rhodium, a preparation method and application thereof, in particular to a preparation method of a pure alpha-phase molybdenum carbide catalyst obtained through one-step carbonization and application thereof in a water-vapor conversion reaction.
Background
The water-gas shift reaction (WGS) is a reaction commonly used in industrial hydrogen production, and is mainly applied to the industries of hydrogen production and ammonia synthesis by taking coal, petroleum and natural gas as raw materials. In the prior catalysts, copper-based and iron-based catalysts are mainly used in industry, and the activity is poor. In recent years, transition metal carbides have become an emerging catalytic material system, with molybdenum carbide being a subject of much attention. Researches show that the alpha-phase molybdenum carbide catalyst shows extremely high activity in the water-gas shift reaction, and is far higher than the beta-phase molybdenum carbide. This is because the alpha-phase molybdenum carbide can activate H2The O-H bond in the O molecule also provides new possibility for hydrogen production by water dissociation.
However, the preparation and application of the alpha-phase molybdenum carbide catalyst are difficult: (1) because the alpha-phase molybdenum carbide is of a face-centered cubic structure (FCC), the preparation method is mostly prepared by a two-step carbonization method of high-temperature ammoniation, cooling and high-temperature carbonization, the method has complex steps and higher cost, high-purity ammonia gas needs to be used for treatment at high temperature in the preparation process, the environmental pollution is very easy to cause, potential safety hazards exist, and the requirement on the corrosion resistance of equipment is very high; (2) alpha-phase molybdenum carbide although for dissociation H2O has an advantage but is also very easily reacted with H2The oxidation of O into molybdenum oxide and further loss of activity, and poor stability is one of the bottleneck problems of the practical application of the alpha-phase molybdenum carbide catalyst.
The patent application of Shichuan et al (patent publication No. CN104923274A) discloses a pure alpha-phase molybdenum carbide supported noble metal catalyst and its preparation method and application, wherein a one-step carbonization method is adopted to synthesize the pure alpha-phase molybdenum carbide catalyst supported by noble metal gold or platinum or palladium, and the obtained crystal form of molybdenum carbide is the pure alpha-phase molybdenum carbide as can be seen from the given XRD spectrogram, but the method needs to carry out non-equilibrium plasma treatment instead of roasting before carbonization, and the method can obtain the pure alpha-phase molybdenum carbide without ammoniation, but the catalyst preparation period is longer and the preparation process is more complicated.
Martin et al published patent application "Pt/alpha-MoC1-xSupported catalysts and their synthesis and use "(patent publication:CN104707636A) adopts a one-step carbonization method to synthesize a noble metal platinum-loaded alpha-phase molybdenum carbide catalyst, and the catalyst is applied to a water-phase methanol reforming reaction, and the given data and XRD spectrogram show that the obtained molybdenum carbide crystal form is pure alpha-phase molybdenum carbide, but the catalyst needs high-temperature roasting treatment in the preparation process, and the noble metal Pt content is high, so that the cost is increased.
The invention provides a method for preparing molybdenum trioxide by adopting a flame spraying method, high-temperature roasting or other pretreatment procedures are not needed in the whole process, the rhodium-loaded molybdenum oxide can be subjected to one-step carbonization to prepare alpha-phase molybdenum carbide, and the alpha-phase molybdenum carbide catalyst with higher purity can be obtained only by trace of noble metal rhodium. The method not only simplifies the preparation process of the alpha-phase molybdenum carbide, reduces the risk of ammonia gas leakage, and reduces the problems of pollution and equipment corrosion, but also obviously improves the activity and stability of the alpha-phase molybdenum carbide in the water-gas shift reaction.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a preparation method for synthesizing pure alpha-phase molybdenum carbide by a one-step carbonization method, aiming at simplifying the synthesis method of the alpha-phase molybdenum carbide, omitting a high-pollution and high-cost ammoniation process required in the preparation process, reducing the risk of environmental pollution and saving the production cost.
In order to achieve the purpose, the invention adopts the following scheme:
the invention provides a preparation method of alpha-phase molybdenum carbide induced by noble metal rhodium, which comprises the following steps:
(1) preparing molybdenum trioxide powder by adopting a flame spraying method;
(2) dipping the molybdenum trioxide powder obtained in the step (1) with a noble metal salt solution to obtain rhodium-loaded molybdenum trioxide;
(3) carbonizing the rhodium-loaded molybdenum trioxide obtained in the step (2) at the temperature of 600 ℃ and 800 ℃ for 1-8 hours under a carbon source gas, wherein CH is contained in the carbon source gas4The volume fraction of (A) is 10-30%, the rest is hydrogen, the flow rate of the mixed gas is 20-500ml/min, and the heating rate is 1-10 ℃/min.
The second technical problem solved by the invention is that the noble metal rhodium-loaded alpha-phase molybdenum carbide catalyst is prepared by the preparation method, wherein the mass percent of Rh is 0.02-5%.
The invention solves the technical problem of providing the application of the noble metal rhodium-loaded alpha-phase molybdenum carbide catalyst in water vapor shift reaction.
The conditions of the noble metal rhodium-loaded alpha-phase molybdenum carbide catalyst for carrying out water vapor shift reaction are as follows, the mass space velocity is 30000-1800000ml/g/H, the volume fraction of CO in the reaction atmosphere is 1-10%, and H is2The volume fraction of O is 2-20%, and the reaction temperature is 120-350 ℃.
The invention has the following beneficial effects:
(1) the molybdenum trioxide prepared by the flame spraying method is small in particle size, is easy to reduce and is beneficial to reducing the carburizing temperature. Meanwhile, the characteristic of noble metal rhodium is utilized to activate H in the carbonization atmosphere2And CH4Greatly reduces the carburizing temperature in the carbonization process of the molybdenum trioxide. The addition of trace rhodium (0.02-0.1 percent by mass) can realize one-step carbonization to prepare high-purity alpha-phase molybdenum carbide, and researches show that the trace rhodium can promote the carbonization process from molybdenum trioxide to MoO with a face-centered cubic structurexCyThe intermediate is converted, thereby further carbonizing to generate alpha-phase molybdenum carbide and inhibiting the molybdenum carbide from passing through MoO2Conversion to beta-Mo2And C, a carbonization route. Compared with the prior art, the method has the advantages of low noble metal amount, high purity of the alpha-phase molybdenum carbide, obvious reduction of the use amount of the noble metal, omission of the high-pollution and high-energy consumption ammoniation process required in the original preparation process of the pure alpha-phase molybdenum carbide, and provision of a new method for the industrial production of the pure alpha-phase molybdenum carbide.
(2) The catalyst prepared by the method has excellent water-vapor conversion performance when only trace noble metal rhodium is added, and experimental results prove that the catalyst has the performance of 10 percent of CO/20 percent of H20.025% Rh/MoO in the reaction atmosphere of O/70% He at 180000ml/g/h space velocity3alpha-MoC obtained by one-step carbonization of catalyst1-xThe reaction rate per unit catalyst at 200 ℃ was 112. mu. molCO/(gcatS) far higher than those using high foulingalpha-MoC prepared by dyeing ammoniation method1-xReaction rate of (3) was 83. mu. molCO/(gcat·s)。
(3) The catalyst prepared by the method can also obviously improve the stability of the alpha-phase molybdenum carbide in the water-vapor transformation reaction. For example, 2% Rh/α -MoC1-xAfter the catalyst reacts for 9 hours at 300 ℃, the CO conversion rate still reaches 70 percent, and the alpha-MoC prepared by the ammoniation method1-xAfter the catalyst reacts for 7 hours, the CO conversion rate is reduced to be below 5 percent.
Drawings
FIG. 1 is the 2% Rh/FSP-. alpha. -MoC obtained in example 11-xExample 2 1% Rh/FSP-MoCxAnd 0.025% Rh/FSP-MoC from example 3xComparing the XRD patterns with that of the pure beta-phase molybdenum carbide obtained in the comparative example 1 and the pure alpha-phase molybdenum carbide prepared by the ammonification method obtained in the comparative example 2;
FIG. 2 shows the 2% Rh/FSP-. alpha. -MoC obtained in example 11-x1% Rh/FSP-MoC from example 2xAnd 0.025% Rh/FSP-MoC from example 3xComparing the activity of the pure beta-phase molybdenum carbide obtained in the comparative example 1 and the activity of the pure alpha-phase molybdenum carbide obtained in the comparative example 2 in the water-vapor shift reaction;
FIG. 3 is the 0.025% Rh/FSP-MoC obtained in example 3x(700 ℃ to 2h carbonization conditions) and 0.025% Rh/FSP-MoC obtained in example 4x(650-8 h carbonization conditions) and 0.025% Rh/FSP-MoC obtained in example 5x(700 ℃ to 0h carbonization conditions) and 0.025% Rh/FSP-MoC obtained in example 6x(600 ℃ -2h carbonization conditions) XRD contrast pattern of the catalyst;
FIG. 4 is the 0.025% Rh/FSP-MoC obtained in example 3x(700 ℃ to 2h carbonization conditions) and 0.025% Rh/FSP-MoC obtained in example 4x(650-8 h carbonization conditions) and 0.025% Rh/FSP-MoC obtained in example 5x(700 ℃ to 0h carbonization conditions) and 0.025% Rh/FSP-MoC obtained in example 6x(600-2 h carbonization condition) the activity of the catalyst for catalyzing the water-vapor shift reaction is compared with that of the catalyst;
FIG. 5 shows the 2% Rh/FSP-. alpha. -MoC obtained in example 11-xA stability comparison graph of the pure alpha-phase molybdenum carbide catalytic water vapor shift reaction obtained in the comparative example 2;
FIG. 6 shows the 2% Rh/FSP-. alpha. -MoC obtained in example 11-xXRD contrast diagram after the pure alpha-phase molybdenum carbide obtained in the comparative example 2 is applied to the stability of catalytic water vapor conversion reaction;
FIG. 7 shows the 2% Rh/FSP-. alpha. -MoC obtained in example 11-xCompared with the pure beta-phase molybdenum carbide obtained in the comparative example 1, the pure alpha-phase molybdenum carbide obtained in the comparative example 2 and the 2 percent Au/FSP-MoC obtained in the comparative example 5xXRD contrast pattern of the catalyst;
FIG. 8 is the 0.025% Rh/FSP-MoC obtained in example 3xCompared with the pure beta-phase molybdenum carbide obtained in the comparative example 1, the pure alpha-phase molybdenum carbide obtained in the comparative example 2, and the 0.025 percent Au/FSP-MoC obtained in the comparative example 3xAnd 0.025% Pt/FSP-MoC obtained in comparative example 4xXRD contrast pattern of the catalyst;
FIG. 9 is a comparison of XRD spectrum changes during the carbonization process of the pure beta-phase molybdenum carbide catalyst obtained in comparative example 1;
FIG. 10 is the 0.025% Rh/FSP-MoC obtained in example 3xComparing the change of XRD spectrogram of the catalyst in the carbonization process;
Detailed Description
The following non-limiting examples will provide those of ordinary skill in the art with a more complete understanding of the present invention, and are not intended to limit the invention in any way.
Example 1
(1) The molybdenum oxide can be prepared by adopting a flame spraying method. The flame spraying method comprises the specific operation steps of dissolving 34.945g of molybdenum acetylacetonate in 100ml of benzyl alcohol, performing ultrasonic stirring for about 1 hour at room temperature to uniformly mix the solution, then adding 100ml of diethyl hexanoic acid (EHA) into the solution, performing ultrasonic stirring for more than about 1 hour at room temperature to uniformly mix the solution as much as possible, and preparing a 0.5mol/L mixed precursor solution; the prepared solution was pumped into the flame using a syringe at a rate of 5 ml/min. The flame combustion gas is a mixed gas composed of methane (0.6L/min) and oxygen (1.9L/min), and the mixed gas is sprayed out from a nozzle with the diameter of 2 mm. Adopting a gas distribution plate (comprising a cylindrical container with one closed end and the other open end, the peripheral edge of the gas distribution plate with gas through holes is connected with the open end of the cylindrical container in a closed way, an air inlet connected with an air pump or an air compressor is arranged on the cylindrical container, and the gas is divided intoCloth plate facing flame) blows a large amount of air (5L/min) into the flame area, combustion products are quickly separated from the flame area under the drive of high-speed air flow, and the sum of the radial cross-sectional areas of the air through holes on the air distribution plate is 3.5 square centimeters. The catalyst particles obtained by combustion were collected using glass fiber filter paper. The prepared catalyst is marked as FSP-MoO with the particle size of 10-30nm3(FSP stands for flame spraying method).
(2) 1ml of 0.04g/ml RhCl was measured3The solution was added to 1g of MoO obtained in step (1)3Adding about 1ml of water (or ethanol) into the sample, and fully and uniformly stirring; standing the sample for 6h, evaporating the sample to dryness in 80 ℃ water bath for 2h to obtain 2% Rh/FSP-MoO3A precursor;
(3) 2 percent of Rh/MoO obtained in the step (2)3Tabletting and molding the precursor sample, preparing into 20-40 mesh particles, weighing 0.13g of the particles, placing the particles in a quartz tube reactor, and placing the particles in the reactor at 20% CH with gas flow rate of 150ml/min4/H2Performing temperature programmed carbonization in the carbonization atmosphere of (V/V), heating from room temperature to 700 ℃, heating at the rate of 5 ℃/min, keeping the temperature at 700 ℃ for 2h, and cooling to room temperature to obtain 2% Rh/FSP-alpha-MoC1-xCatalyst (0)<x<1，α-MoC1-xMolybdenum carbide representing a pure alpha phase, the same applies below);
(4) and (3) directly carrying out the water-vapor shift reaction in a quartz tube reactor in the carbonization step, directly cutting the catalyst obtained in the step (2) from the carbonized gas into inert gas for replacement, and then cutting into reaction gas for carrying out the in-situ water-vapor shift reaction. The composition of the reaction gas used for water-vapor transformation is 5% CO/20% H2O/75% He (V/V/V), the gas mass space velocity of 30000ml/g/h and the reaction temperature of 120-;
(5) as the activity of the catalyst is gradually improved along with the increase of the reaction temperature, the activity reaches a peak value about 200 ℃, then the temperature is continuously increased, the activity of the catalyst is reduced, and the activity of the catalyst at 200 ℃ exceeds 90%;
to compare the activity difference at this temperature for catalysts with different Rh loadings, the activity change of the catalyst was measured by raising the space velocity at 200 ℃ and varying the CO and H2And the proportion of O, and the change of the CO conversion rate is observed. Are specifically required to be respectivelyThe following procedure was carried out under the following operating conditions,
the method comprises the following steps: 200 ℃, reaction gas composition: 5% CO/20% H2O/75% He (V/V/V), space velocity modulation: 30000 → 60000 → 120000 → 180000 ml/g/h;
secondly, the step of: 200 ℃, reaction gas composition: 10% CO/20% H2O/70% He (V/V/V), space velocity: 180000 ml/g/h.
Example 2
The steps and process conditions of this example are the same as those of example 1, and are different from them only in the following point: 0.5ml of 0.04g/ml RhCl was measured3The solution was added to 1g of MoO3In the preparation, 1 percent of Rh/MoC is loaded by mass percentxA catalyst.
Example 3
The steps and process conditions of this example are the same as those of example 1, and are different from those of example 1 only in the following point: 0.31ml of 1.6mg/ml RhCl was measured3The solution was added to 1g of MoO3In the preparation, Rh/MoC with the load mass percent of 0.025 percent is preparedxA catalyst.
Example 4
The steps and process conditions of this example were the same as those of example 3, and the difference therebetween was only the following point: the temperature of the carbonization process is increased from room temperature to 650 ℃, the temperature increasing rate is 5 ℃/min, and the temperature is kept at 650 ℃ for 8 h.
Example 5
The steps and process conditions of this example were the same as those of example 3, and the difference therebetween was only the following point: the temperature is raised from room temperature to 700 ℃ at a rate of 5 ℃/min, but not at 700 ℃.
Example 6
The steps and process conditions of this example were the same as those of example 3, and the difference therebetween was only the following point: heating from room temperature to 600 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature at 600 ℃ for 2 h.
Comparative example 1
(1) The molybdenum oxide can be prepared by adopting a flame spraying method. The specific operation of the flame spraying method is the same as that of the step (1) of the example 1;
(2) MoO obtained in the step (1)3Tabletting and molding, making into 20-40 mesh granules, weighing 1g, placing in a quartz tube reactor, and introducing 20% CH with gas flow rate of 150ml/min4/H2Performing temperature programmed carbonization in (V/V) atmosphere, heating from room temperature to 700 deg.C at a heating rate of 5 deg.C/min, maintaining at 700 deg.C for 2h, and rapidly cooling to room temperature in carbonization atmosphere to obtain FSP-beta-Mo2C catalyst (beta-Mo)2C represents pure beta-phase molybdenum carbide);
(3) and (3) directly carrying out water-vapor shift reaction in a quartz tube reactor in the carbonization step, directly cutting the catalyst obtained in the step (3) from the carbonized gas into inert gas for replacement, and then cutting into reaction gas for carrying out in-situ water-vapor shift reaction. The composition of the reaction gas used for water-vapor transformation is 5% CO/20% H2O/75% He (V/V/V), gas mass space velocity of 30000ml/g/h, reaction temperature of 120-. In each gas switching process, inert gas N is needed2The gas in the reactor was purged for about 10min to ensure safety.
Comparative example 2
(1) The molybdenum oxide can be prepared by adopting a flame spraying method. The specific operation of the flame spraying method is the same as that of the step (1) of the example 1;
(2) MoO obtained in the step (1)3Tabletting and molding, preparing into 20-40 mesh granules, weighing 1g, placing in a quartz tube reactor, and introducing pure NH with gas flow rate of 150ml/min3In the atmosphere of (2), performing temperature programmed ammonification, heating from room temperature to 700 ℃, with the heating rate of 5 ℃/min, keeping the temperature at 700 ℃ for 2h, and then NH3Rapidly cooling to room temperature under the atmosphere;
(3) the gas was then switched to 20% CH4/H with a gas flow rate of 150ml/min2(V/V), carrying out programmed temperature rise carbonization again in the carbonization atmosphere, raising the temperature from room temperature to 700 ℃, keeping the temperature at 700 ℃ for 2h at the temperature raising rate, and then rapidly cooling to the room temperature in the carbonization atmosphere;
(4) finally, at normal temperature, the gas was switched to 1% O at a gas flow rate of 50ml/min2Performing passivation on/Ar (V/V) for 12 hours to obtain FSP-alpha-MoC1-xA catalyst.In each gas switching process, inert gas N is needed2Purging the gas in the reactor for about 10min to ensure safety;
(5) since the ammoniation treatment has high requirements for the carbonization equipment, the ex-situ steam shift evaluation is adopted here. The water-vapor shift reaction is directly carried out in another quartz tube reactor, and the sample pretreatment condition is 20% CH at 50ml/min4/H2The temperature was programmed from room temperature to 700 ℃ at a temperature rise rate of 5 ℃/min under an atmosphere and held at that temperature for 2 hours, and then, the temperature was rapidly lowered to room temperature under that atmosphere. Cutting carbonized gas into inert gas for replacement, and cutting into reaction gas for in-situ water-vapor conversion reaction.
The composition of the reaction gas used for water-vapor transformation is 5% CO/20% H2The content of the O/75% He is 300-350 ℃, the gas mass space velocity is 30000ml/g/h, and the reaction temperature is 120-;
(6) the space velocity adjusting step was the same as in step (5) of example 1.
Comparative example 3
The procedure and process conditions of this example were the same as those of example 1, except for the following points: 0.56ml of 0.38mg/ml H was measured2AuCl4The solution was added to 1g of MoO3In the preparation, Au/FSP-MoC with the load mass percentage of 0.025 percent is preparedxA catalyst.
Comparative example 4
The procedure and process conditions of this example were the same as those of example 1, except for the following points: 0.125ml of 2mg/ml (NH) was measured4)2PtCl6The solution was added to 1g of MoO3In the preparation, Pt/FSP-MoC with the load mass percentage of 0.025 percent is preparedxA catalyst.
Comparative example 5
The steps and process conditions of this example are the same as those of example 1, except for the following points: 3.6ml of 9.57mg/ml H were measured2AuCl4The solution was added to 1g of MoO3In the preparation process, Au/FSP-MoC with the load mass percentage of 2 percent is preparedxA catalyst.
The noble metal rhodium-loaded alpha-phase molybdenum carbide catalyst pair in the inventionThe water-vapor shift reaction has excellent catalytic performance; the catalytic performance is still better under the conditions of high space velocity and low temperature, and the experimental result proves that the catalyst is prepared from 10 percent of CO/20 percent of H20.025% Rh/alpha-MoC from example 3 in a reaction atmosphere of O/70% He at a space velocity of 180000ml/g/h1-xThe reaction rate of the catalyst is 112 mu mol at 200 DEG CCO/(gcatS) is superior to beta-Mo2MoC of C and mixed crystal of alpha phase and beta phasexThe water-gas shift reaction activity of (1). In addition, when the loading amount of rhodium is more than 1%, the method can promote the generation of pure alpha-phase molybdenum carbide, obviously improve the stability of the pure alpha-phase molybdenum carbide in the water-vapor conversion reaction and inhibit the molybdenum carbide from being oxidized. For example, 2% Rh/α -MoC1-xThe catalyst still had 79.6% activity at 350 c, whereas the pure alpha phase molybdenum carbide catalyst had only 10.2% activity at 350 c. In conclusion, the method is a promising invention technology in the fields of pure alpha-phase molybdenum carbide preparation and water-vapor transformation application.
TABLE 1 comparison of the reaction rates of the catalysts prepared according to the invention in the water-gas shift reaction with the catalysts known from the literature
a 11％CO/26％H2O/26％H2/7％CO2/He；
b 11％CO/21％H2O/43％H2/6％CO2/N2；
c 11％CO/26％H2O/26％H2/7％CO2/30％N2；
d 1 bar CO/NaOH solution；
e 10％CO/20％H2O/He 。
Claims (9)
1. The method for preparing the pure alpha-phase molybdenum carbide catalyst by one-step carbonization is characterized by comprising the following steps:
1) preparing molybdenum trioxide by a flame spraying method: dissolving an organic precursor containing molybdenum in an organic solvent to obtain a precursor solution, dispersing the precursor solution into liquid drops, introducing the liquid drops into flame for combustion, and collecting molybdenum trioxide powder formed after the combustion;
2) loading noble metal rhodium: dipping (preferably dipping in the same volume) the molybdenum trioxide powder obtained in the step (1) in a salt solution of noble metal rhodium, stirring, standing and evaporating to dryness to obtain rhodium-loaded molybdenum trioxide;
3) one-step carbonization: carbonizing the rhodium-loaded molybdenum trioxide prepared in the step (2) under a carbon source gas.
2. The method according to claim 1, wherein the precursor compound of molybdenum in the step (1) of preparing molybdenum trioxide by flame spraying is a compound soluble in an organic solvent, preferably one or more of ammonium molybdate, molybdenum acetylacetonate, molybdenum nitrate and molybdenum 2-ethylhexanoate; the solvent is a combustible organic solvent, preferably one or more of methanol, ethanol, xylene, benzyl alcohol and organic acid.
3. The method of claim 1, wherein: the combustion gas required by the flame combustion in the step (1) is a mixed gas of methane and oxygen, and the flow rates of the methane and the oxygen are both 0.1-10L/min; the speed of pumping the precursor solution into the flame is 0.1-20 ml/min.
4. The method of claim 3, wherein:
in the step (1), the mixed gas is sprayed out from a nozzle with the diameter of 1-10mm to form flame, and air is blown into one side of the flame; the flame ignites the introduced organic solution, precursor compounds of each component are decomposed at high temperature of the flame to form oxide particles, the formed oxide particles leave a flame area under the drive of air, the air is blown to the whole flame area from one side of the flame by a gas distribution plate or a sieve plate with uniformly distributed gas through holes on the surface, the sum of the radial cross-sectional areas of the gas through holes on the gas distribution plate or the sieve plate is 0.1-10 square centimeters, and the air flow is 0.1-20L/min.
5. The method according to claim 1, wherein the impregnation method in step (2) is preferably an equal volume impregnation; the concentration of the rhodium salt solution is 1-100mg/ml, and the standing time is 6-24h, preferably 12-24 h; the drying temperature is 60-200 deg.C, preferably 80-150 deg.C, and the drying time is 1-20 hr, preferably 4-12 hr; the rhodium salt solution is RhCl3An aqueous solution of (a); the mass loading of rhodium in the rhodium-loaded molybdenum trioxide is 0.02-5%.
6. The method as claimed in claim 1, wherein the carbon source in step (3) is a mixed gas of methane and hydrogen, the methane accounts for 10-30% of the whole mixed gas by volume, the flow rate of the mixed gas is 20-500ml/min, the temperature rising rate from room temperature to the carbonization temperature is 1-10 ℃/min, the carbonization temperature is 600-800 ℃, and the carbonization time is 1-8 hours.
7. An alpha-phase molybdenum carbide catalyst loaded with noble metal rhodium, which is prepared by the preparation method of any one of claims 1 to 6.
8. Use of the catalyst of claim 7 in a water-gas shift reaction.
9. The use of the catalyst as claimed in claim 8, wherein the conditions of the water vapor shift reaction are that the mass space velocity is 30000-180000ml/g/H, the volume ratio of CO in the reaction atmosphere is 1-10%, and H is2The volume ratio of O is 2-20%, the rest is one or more than two of nitrogen or inert gases, and the reaction temperature is 120-350 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080268246A1 (en) * | 2005-09-06 | 2008-10-30 | Eth Zurich | Methods and Devices for Flame Spray Pyrolysis |
| CN102698783A (en) * | 2012-05-30 | 2012-10-03 | 大连理工大学 | Method for preparing metal-modified alpha type molybdenum carbide catalyst and application of metal-modified alpha type molybdenum carbide catalyst in low-temperature water-gas shift reaction |
| CN104923274A (en) * | 2015-05-18 | 2015-09-23 | 大连理工大学 | Pure alpha-phase molybdenum carbide-loaded noble metal catalyst, and preparation method and application thereof |
| CN105161700A (en) * | 2015-08-05 | 2015-12-16 | 华东理工大学 | Molybdenum trioxide coated molybdenum doped titanium dioxide nano composite particle and preparation method and application thereof |
| CN105540588A (en) * | 2015-12-08 | 2016-05-04 | 大连理工大学 | Application of alpha-molybdenum carbide and metal-modified alpha-molybdenum carbide catalyst to reaction for preparing carbon monoxide through hydrogenation of carbon dioxide |
| CN107500296A (en) * | 2017-09-20 | 2017-12-22 | 大连理工大学 | A kind of bar-shaped β Mo2C controlledly synthesis and its application in inverse water gas shift reation |
-
2021
- 2021-01-04 CN CN202110003270.8A patent/CN114713253B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080268246A1 (en) * | 2005-09-06 | 2008-10-30 | Eth Zurich | Methods and Devices for Flame Spray Pyrolysis |
| CN102698783A (en) * | 2012-05-30 | 2012-10-03 | 大连理工大学 | Method for preparing metal-modified alpha type molybdenum carbide catalyst and application of metal-modified alpha type molybdenum carbide catalyst in low-temperature water-gas shift reaction |
| CN104923274A (en) * | 2015-05-18 | 2015-09-23 | 大连理工大学 | Pure alpha-phase molybdenum carbide-loaded noble metal catalyst, and preparation method and application thereof |
| CN105161700A (en) * | 2015-08-05 | 2015-12-16 | 华东理工大学 | Molybdenum trioxide coated molybdenum doped titanium dioxide nano composite particle and preparation method and application thereof |
| CN105540588A (en) * | 2015-12-08 | 2016-05-04 | 大连理工大学 | Application of alpha-molybdenum carbide and metal-modified alpha-molybdenum carbide catalyst to reaction for preparing carbon monoxide through hydrogenation of carbon dioxide |
| CN107500296A (en) * | 2017-09-20 | 2017-12-22 | 大连理工大学 | A kind of bar-shaped β Mo2C controlledly synthesis and its application in inverse water gas shift reation |
Non-Patent Citations (1)
| Title |
|---|
| KIRSTEN SCHUH ET AL.: "Systematic study on the influence of the morphology of α-MoO3 in the selective oxidation of propylene", 《JOURNAL OFSOLIDSTATECHEMISTRY》, vol. 228, pages 42 - 52 * |
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