CN109433202B - Ruthenium-based catalyst loaded on barium tantalate surface and application thereof in ammonia synthesis - Google Patents

Ruthenium-based catalyst loaded on barium tantalate surface and application thereof in ammonia synthesis Download PDF

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CN109433202B
CN109433202B CN201811246294.0A CN201811246294A CN109433202B CN 109433202 B CN109433202 B CN 109433202B CN 201811246294 A CN201811246294 A CN 201811246294A CN 109433202 B CN109433202 B CN 109433202B
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ruthenium
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barium tantalate
nitrate
acetate
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CN109433202A (en
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游志雄
黄佳
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Wuhan University WHU
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/648—Vanadium, niobium or tantalum or polonium
    • B01J23/6486—Tantalum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention provides a ruthenium-based catalyst loaded on the surface of barium tantalate and application thereof in ammonia synthesis, belonging to the field of catalysis. Barium tantalate is used as a carrier, active ingredient ruthenium is loaded on the surface of the barium tantalate, wherein the mass ratio of Ru to barium tantalate is (0.1-16): 100, the specific surface area of the barium tantalate is 10-50m2(ii) in terms of/g. The preparation method is simple, and the ammonia synthesis catalyst carrier can be prepared through simple hydrothermal reaction. The catalyst prepared by the invention has high catalytic activity, good stability and high safety performance.

Description

Ruthenium-based catalyst loaded on barium tantalate surface and application thereof in ammonia synthesis
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a ruthenium-based catalyst loaded on the surface of barium tantalate and application thereof in ammonia synthesis.
Background
The synthetic ammonia industry is one of the most important chemical industries, and countries around the world are working on the development of the synthetic ammonia industry. The synthetic ammonia is an effective artificial nitrogen fixation means and provides 40-60% of nitrogen source for human body. Ammonia is readily liquefied (0.86MPaat 20 ℃ or-33.4 ℃ at 0.1MPa) and is carbon-free, so ammonia is considered to be one of the closest practical renewable fuels and also an important hydrogen energy carrier that can reconcile energy and environmental issues. In 1913, Haber-Bosch ammonia synthesis iron catalyst and its process flow in German Aubo ((Oppau) for the first time realized industrialization, making the ammonia synthesis method from cyanidation to nitrogen-hydrogen mixture synthesis ammonia process, thereby greatly improving the ammonia yield is known as the first generation ammonia synthesis catalyst. Haber-Bosch process operating conditions generally at 400- The catalyst is used for replacing the traditional iron catalyst, so that the requirement of the traditional Haber-Bosch process is improved, and the requirement of meeting the future ammonia new energy challenge is met.
Currently, the active components of the ammonia synthesis catalyst are Fe, Ru, Co, Ni and the like, and the carriers are MgO and Al2O3、Nb2O5、TiO2Activated carbon, electronic salts, and the like. The most rate-limiting step in ammonia synthesis is nitrogen dissociation, Ru is widely used for ammonia synthesis due to its excellent nitrogen dissociation capability, and in 1992, a ruthenium catalyst with activated carbon as a carrier is first industrialized in an Ocelot ammonia plant in Canada. However, under the ammonia synthesis reaction conditions, the ruthenium metal tends to methanize the activated carbon support, resulting in a decrease in the catalyst activity, limiting the large-scale industrial application of ruthenium catalysts. In addition, the carbon material also has inflammability and has certain potential safety hazard when being used in industry. Therefore, it remains an important subject to provide a ruthenium-based catalyst support that is chemically stable and safe to use. Barium tantalate has excellent photoelectric and nonlinear optical properties, and good optical and electrical properties, and thus is widely used in the fields of photocatalysis, laser, batteries, and the like. But the application in the aspect of ammonia synthesis has never been reported.
Disclosure of Invention
In order to solve the problems, the invention loads ruthenium on the surface of barium tantalate to prepare the synthetic ammonia catalyst with high catalytic activity, good stability and safe use.
The technical scheme provided by the invention is as follows:
the ruthenium-based catalyst loaded on the surface of barium tantalate uses barium tantalate as a carrier, and the surface of the barium tantalate loads active ingredient ruthenium, wherein the mass ratio of Ru to barium tantalate is (0.1-16): 100, the specific surface area of the barium tantalate is 10-50m2/g。
Preferably, the structure of the barium tantalate is Ba5Ta4O15。
Preferably, the barium tantalate is prepared by the following method: the molar ratio of Ba to Ta is (8-12): 1, and heating the mixture at 150-220 ℃ for 140-180 h.
Preferably, the Ta precursor is one or more of oxides, hydroxides and salts of Ta, and the Ba precursor is one or more of oxides, hydroxides and salts of Ba.
In the preparation process of the barium tantalate carrier, the preparation method can be based on the preparation of tantalum and bariumDifferent precursors, solvent capable of dissolving or dispersing corresponding precursor such as water, alcohol, and supercritical CO is selected2And the like or a mixture of more than one thereof; the synthesis reaction is preferably carried out in a closed reaction system (such as an autoclave), and the reaction temperature is preferably between 150 ℃ and 220 ℃, more preferably between 180 ℃ and 200 ℃. The reaction time is preferably 140-180 h, and the preferable reaction time is 150-170 h; the reaction time is too short, and precursors of tantalum and barium are not reacted sufficiently, so that an ideal carrier cannot be obtained; too long a reaction time increases the energy consumption of the synthesis process. The synthesized catalyst carrier can be recovered from the sample obtained by the reaction by common solid-liquid separation means (such as filtration, centrifugation and the like), and then dried by conventional drying means (such as airing, drying, freeze drying, vacuum drying and the like).
The invention also provides a preparation method of the ruthenium-based catalyst, which comprises the following steps: dispersing barium tantalate carriers in a ruthenium precursor solution, wherein the mass ratio of Ru in the ruthenium precursor solution to barium tantalate carriers is (0.1-16): 100, stirring, then spin-drying the solvent, placing the obtained mixture in a quartz tube, heating to 150-400 ℃, and treating for 2-20h in an inert gas atmosphere or vacuum to obtain the ruthenium-based catalyst.
The loading rate of ruthenium on the surface of barium tantalate is 0.1-16% of the mass of the barium tantalate carrier; if the loading rate is lower than 0.1%, the catalytic action of the catalyst on the synthetic ammonia is not obvious; if the ruthenium loading rate is higher than 16%, the ruthenium particles may have too large a particle diameter, which may decrease the catalytic efficiency per ruthenium.
Preferably, the ruthenium precursor is Ru3(CO)12、Ru(CH3COCHCOCH3)3、Ru(CH3COO)3、Ru(NO)(NO3)3、RuCl3One or more of them.
The invention also provides another ruthenium-based catalyst loaded on the surface of barium tantalate, and the promoter metal compound is loaded on the ruthenium-based catalyst.
Preferably, on the basis of loading ruthenium on the surface of barium tantalate, the catalytic performance of the catalyst is improved by adding a proper amount of one or more of alkali metal, alkaline earth metal and rare earth metal as an auxiliary agent. The addition amount of the alkali metal, alkaline earth metal and rare earth metal additive is preferably 0 to 16 times the mole number of ruthenium supported on the surface of barium tantalate. The addition of a small amount of promoter metal compound is beneficial to the distribution of the promoter around the active ruthenium nano-particles, thereby effectively promoting the catalytic performance of ruthenium. The addition amount is not more than 16 times, so that the ruthenium nano particles on the surface of the catalyst are prevented from being completely covered by the auxiliary agent, and a reactant is prevented from contacting with ruthenium surface atoms to reduce the catalytic activity of the ruthenium nano particles.
Preferably, the alkali metal compound is one or more of sodium acetate, potassium acetate, rubidium acetate, cesium acetate, sodium nitrate, potassium nitrate, rubidium nitrate and cesium nitrate; the alkaline earth metal compound is one or more of calcium acetate, barium acetate, strontium acetate, calcium nitrate, barium nitrate and strontium nitrate; the rare earth metal compound is one or more of lanthanum acetate, samarium acetate, cerium acetate, lanthanum nitrate, samarium nitrate and cerium nitrate. Specifically, NaOH, KOH, RbOH, CsOH, CaO, SrO, BaO, La, etc. may be added2O3、CeO2、Sm2O3And the like as an auxiliary agent.
The preparation method of the ruthenium-based catalyst loaded with the assistant metal compound comprises the following steps: and (2) soaking the ruthenium-based catalyst in a solution containing an auxiliary agent metal compound, removing the solvent, and drying to obtain the auxiliary agent metal compound-loaded ruthenium-based catalyst.
The invention also provides the application of the ruthenium-based catalyst in the field of ammonia synthesis, and the reaction conditions of the catalyst used in the catalytic reaction of ammonia synthesis are as follows: the temperature is 250 ℃ and 500 ℃, the pressure is 0.1-5.1 MPa, and the space velocity is 1000-1000000.
The invention utilizes the catalyst to lead N to be generated under certain temperature, pressure and space velocity2And H2The reaction takes place to generate ammonia. The temperature of the ammonia synthesis reaction is preferably set within the range of 250 ℃ to 500 ℃. The reaction temperature is higher than 250 ℃ in order to ensure that the ruthenium catalyzes the activation speed of the nitrogen molecules to be fast enough. In addition, the reaction temperature is set to 500 ℃ or lower in order to prevent deterioration of the ruthenium active component. Ammonia synthesisThe reaction pressure is suitably set within the range of 0.1-5.1 MPa. Pressures above 0.1MPa favor a shift in the reaction equilibrium towards the opposite of the ammonia production. The pressure is not higher than 5.1MPa, and the energy consumption caused by boosting can be saved. The space velocity (GHSV) of the ammonia synthesis reaction is preferably selected within the range of 1000 to 1000000. The GHSV is set to be more than 1000, so that the generated ammonia gas can be effectively prevented from being decomposed into nitrogen and hydrogen again. And the GHSV set below 1000000 can save the energy consumed for circulating the unreacted gas.
The principle of the invention is as follows:
the low-price tantalum can activate nitrogen, but the tantalum is difficult to transfer to the low price under the condition of synthesizing ammonia, and the high-price tantalum can be transferred to the low price when Ru is loaded on the surface, so that the activity of synthesizing ammonia is further improved. The existence of barium tantalate has the promotion effect on the ammonia synthesis activity of the ruthenium-based catalyst, and Ba5Ta4O15The carrier is of a nano-sheet structure, Ru is on Ba5Ta4O15Growth on the support exposes more active sites and thus allows for higher catalytic activity. The invention has the following advantages and beneficial effects:
(1) the preparation method is simple, and the ammonia synthesis catalyst carrier can be prepared through simple hydrothermal reaction.
(2) The catalyst prepared by the invention has high catalytic activity, good stability and high safety performance.
Drawings
FIG. 1 shows barium tantalate Ba obtained in example 15Ta4O15SEM spectra of the vector;
FIG. 2 shows barium tantalate Ba obtained in example 15Ta4O15An XRD pattern of the support;
fig. 3 is a graph showing the effect of the catalytic stability test on the catalyst prepared in example 2.
Detailed Description
The invention will now be described in more detail by way of examples. The embodiments do not limit the scope of the present invention, and all equivalent results or equivalent process changes made by using the contents and ideas of the present specification, or other related fields directly or indirectly are included in the scope of the present invention.
Example 1:
Ba5Ta4O15preparation of the support
(1) Taking 6.3g Ba (OH)2·8H2O and 0.55g Ta2O5Dissolved in 45mL of an aqueous solution and stirred for 60 min.
(2) The mixed solution obtained in (1) was transferred to a 100mL reaction vessel containing polytetrafluoroethylene. The reaction temperature was set at 200 ℃ and the reaction time was 168 h.
(3) After the reaction, the white substance is centrifuged, washed and dried to obtain Ba5Ta4O15The carrier is a flower-like structure assembled by nano sheets as shown in fig. 1, and the growth of Ru on the carrier with a sheet structure is easier to be flat, and compared with the round shape, the flat shape can expose more active sites and thus can obtain higher catalytic activity. The analysis of the obtained product by XRD showed that the comparative analysis of PDF (72-0115) card showed Ba in the structure shown in FIG. 25Ta4O15The barium tantalate support.
Preparation of ruthenium-based catalysts
(1) 0.0315g of dodecacarbonyl triruthenium was dissolved in 10mL of tetrahydrofuran, and 0.5012g of the obtained Ba was added after the dodecacarbonyl triruthenium was dissolved5Ta4O15The carrier was stirred for 5h and then rotary evaporated for 3h to give a mixture.
(2) And (3) putting the mixture obtained in the last step into a quartz tube, heating to 200 ℃ at the speed of 5 ℃/min, reducing and removing carbonyl under the argon atmosphere for 9-11 h to obtain the ruthenium-based catalyst.
(3) And (3) granulating the ruthenium-based catalyst, taking 0.1013g of the ruthenium-based catalyst with the particle size range of 0.22-0.45 micrometer, filling the ruthenium-based catalyst into a quartz tube, and carrying out a catalytic activity test.
Ammonia synthesis catalyzed by ruthenium-based catalyst
The ammonia synthesis rate is calculated by adopting a method of absorbing ammonia by sulfuric acid and changing the conductivity of sulfuric acid.
200mL of sulfuric acid was dissolvedLiquid (c (H)2SO4) 0.00108mol/L) was poured into a 250mL three-necked flask, the stirrer speed was adjusted to 30rpm, and the water bath temperature was adjusted to 30 ℃.
At an air flow rate ratio of 3: 1 introduction of H2/N2，H2：45mL/min，N2: 15mL/min, and the pressure is 0.1 MPa. After reduction for 3h at 400 ℃, the catalytic activity of different temperature points is measured by a temperature programming curve. And (3) reaching the temperature point of each test, stabilizing for 30min and carrying out the test, wherein the test time is 30min, and the test results are shown in the following table 1.
TABLE 1 Ammonia Synthesis Rate (. mu. mol. g) for different test temperature points-1 cat·h-1) Wherein the mass ratio of Ru to barium tantalate carrier is 1.96: 100.
Figure BDA0001840589150000051
ammonia synthesis activity test of ruthenium-based catalysts with different loading rates
Respectively dissolving 0.0212g, 0.0315g and 0.0424g of dodecacarbonyl triruthenium in 10mL of tetrahydrofuran, adding 0.5003g of Ba5Ta4O15And (3) a carrier. After stirring for 5h, rotary evaporation was carried out for 3h to give a mixture. And (3) putting the mixture obtained in the last step into a quartz tube, heating to 200 ℃ at the speed of 5 ℃/min, reducing and removing carbonyl under the atmosphere of argon for 9-11 h to obtain the ruthenium-based catalyst. And (3) granulating the ruthenium-based catalyst, and loading 0.1001-0.1013 g of the ruthenium-based catalyst with the particle size range of 0.22-0.45 micrometer into a quartz tube for a catalytic activity test.
The ammonia synthesis rate is calculated by adopting a method of absorbing ammonia by sulfuric acid and changing the conductivity of sulfuric acid.
200mL of sulfuric acid solution (c (H)2SO4) 0.00108mol/L) was poured into a 250mL three-necked flask, the stirrer speed was adjusted to 30rpm, and the water bath temperature was 30 ℃.
At an air flow rate ratio of 3: 1 introduction of H2/N2，H2：45mL/min，N2: 15mL/min, and the pressure is 0.1 MPa. The process is carried out after the reduction is carried out for 3 hours at 400 DEG CThe temperature sequence curve measures the catalytic activity at different temperature points. And (3) stabilizing for 30min after reaching the temperature point of each test, and then performing the test, wherein the test time is 30min, and the test results are shown in the following table 2.
TABLE 2 Ammonia Synthesis Rate (. mu. mol. g) of ruthenium-based catalysts with different Ru to barium tantalate support mass ratios (1-3: 100)-1 cat·h-1)
Figure BDA0001840589150000052
Example 2
Addition of the auxiliary agent CsNO3Preparation of ruthenium-based catalyst
0.0315g of triruthenium dodecacarbonyl is dissolved in 10mL of tetrahydrofuran, and 0.5012g of Ba is added after triruthenium dodecacarbonyl is dissolved5Ta4O15The carrier was stirred for 5h and then rotary evaporated for 3h to give a mixture. And (3) putting the mixture obtained in the last step into a quartz tube, heating to 200 ℃ at the speed of 5 ℃/min, reducing and removing carbonyl under the atmosphere of argon for 9-11 h to obtain the ruthenium-based catalyst.
Respectively adding the following components in a molar ratio of Cs: ru is 1: 1. 2: 1. 3: 1. 4: 1 addition of CsNO310mL of distilled water was added, and after cesium nitrate was dissolved, 0.1505g of ruthenium-based catalyst was added, followed by stirring for 5 hours and rotary evaporation to obtain a mixture. And (3) granulating the product obtained in the last step, taking 0.1005g of catalyst with the particle size range of 0.22-0.45 micrometer, filling the catalyst into a quartz tube, and carrying out a catalytic activity test.
The ammonia synthesis rate is calculated by adopting a method of absorbing ammonia by sulfuric acid and changing the conductivity of sulfuric acid.
200mL of sulfuric acid solution (c (H)2SO4) 0.00108mol/L) was poured into a 250mL three-necked flask, the stirrer speed was adjusted to 30rpm, and the water bath temperature was 30 ℃. At an air flow rate ratio of 3: 1 introduction of H2/N2，H2：45mL/min，N2: 15mL/min, and the pressure is 0.1 MPa. After reduction for 3h at 400 ℃, the catalytic activity of different temperature points is measured by a temperature programming curve. When the temperature point of each test is reached, the test is waited for 30min firstly and then tested for 30min, and the test results are shown in the following table3, respectively.
TABLE 3 Ammonia Synthesis Rate (. mu. mol. g) for catalysts with different loadings of auxiliary-1 cat·h-1)
Figure BDA0001840589150000061
Addition of the auxiliary agent CsNO3Stability test of the catalyst
Taking a molar ratio Cs: ru is 3: 1, performing a catalytic activity stability test, and calculating the ammonia synthesis rate by adopting a method of absorbing ammonia by sulfuric acid and changing the conductivity of sulfuric acid.
200mL of sulfuric acid solution (c (H)2SO4) 0.00108mol/L) was poured into a 250mL three-necked flask, the stirrer speed was adjusted to 30rpm, and the water bath temperature was 30 ℃. At an airflow rate of 3: 1 introduction of H2/N2，H2：45mL/min，N2: 15mL/min, and the pressure is 0.1 MPa. The temperature is increased to 400 ℃, reduction is carried out for 3h, then stability test is carried out for 72h at 400 ℃, the ammonia synthesis rate is tested every 2h for 30min, and the stability test result is shown in figure 3.

Claims (9)

1. The ruthenium-based catalyst loaded on the surface of barium tantalate is characterized in that barium tantalate is used as a carrier, and ruthenium serving as an active ingredient is loaded on the surface of the barium tantalate, wherein the mass ratio of Ru to barium tantalate is (0.1-16): 100, the specific surface area of the barium tantalate is 10-50m2The structure is a nano sheet structure with the structural formula of Ba5Ta4O15。
2. The ruthenium-based catalyst according to claim 1, wherein the barium tantalate is prepared by the following method: the molar ratio of Ba to Ta is (8-12): 1, and heating the mixture at 150-220 ℃ for 140-180 h.
3. The ruthenium-based catalyst according to claim 2, wherein the Ta precursor is one or more of an oxide, a hydroxide and a salt of Ta, and the Ba precursor is one or more of an oxide, a hydroxide and a salt of Ba.
4. A method for preparing a ruthenium-based catalyst according to any one of claims 1 to 3, comprising the steps of: dispersing a barium tantalate carrier in a ruthenium precursor solution, wherein the mass ratio of Ru in the ruthenium precursor solution to the barium tantalate carrier is (0.1-16): 100, stirring, then spin-drying the solvent, placing the obtained mixture in a quartz tube, heating to 150-400 ℃, and treating for 2-20h in an inert gas atmosphere or vacuum to obtain the ruthenium-based catalyst.
5. The method according to claim 4, wherein the ruthenium precursor is Ru3(CO)12、Ru(CH3COCHCOCH3)3、Ru(CH3COO)3、Ru(NO)(NO3)3、RuCl3One or more of them.
6. A ruthenium-based catalyst supported on the surface of barium tantalate, wherein a promoter metal compound is supported on the ruthenium-based catalyst according to any one of claims 1 to 3.
7. The ruthenium-based catalyst according to claim 6, wherein the promoter metal compound is one or more of an alkali metal compound, an alkaline earth metal compound and a rare earth metal compound, and the molar ratio of the promoter metal compound to ruthenium is not more than 16: 1.
8. the ruthenium-based catalyst according to claim 7, wherein the alkali metal compound is one or more of sodium acetate, potassium acetate, rubidium acetate, cesium acetate, sodium nitrate, potassium nitrate, rubidium nitrate, and cesium nitrate; the alkaline earth metal compound is one or more of calcium acetate, barium acetate, strontium acetate, calcium nitrate, barium nitrate and strontium nitrate; the rare earth metal compound is one or more of lanthanum acetate, samarium acetate, cerium acetate, lanthanum nitrate, samarium nitrate and cerium nitrate.
9. Use of ruthenium-based catalyst according to any one of claims 1 to 3, 6 to 8 in the field of ammonia synthesis, characterized in that the catalytic reaction conditions are as follows: the temperature is 250-: 1000 to 1000000 hours-1。
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CN102658135A (en) * 2012-05-02 2012-09-12 福州大学 Ruthenium supported perovskite-type-oxide ammonia synthesis catalyst and preparation method thereof
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WO2012159051A2 (en) * 2011-05-19 2012-11-22 Research Foundation Of The City University Of New York Chemically modified graphene
CN102658135A (en) * 2012-05-02 2012-09-12 福州大学 Ruthenium supported perovskite-type-oxide ammonia synthesis catalyst and preparation method thereof
KR101724547B1 (en) * 2017-03-02 2017-04-07 서강대학교산학협력단 Membrane for transporting hydrogen ion, membrane for producing hydrogen, and preparing method of the same

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