CN108993487B - It is catalyzed nitrogen under a kind of room temperature and hydrogen generates the method for preparing catalyst of ammonia - Google Patents

It is catalyzed nitrogen under a kind of room temperature and hydrogen generates the method for preparing catalyst of ammonia Download PDF

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CN108993487B
CN108993487B CN201810798775.6A CN201810798775A CN108993487B CN 108993487 B CN108993487 B CN 108993487B CN 201810798775 A CN201810798775 A CN 201810798775A CN 108993487 B CN108993487 B CN 108993487B
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ruthenium
trimethyl
platinum
catalyst
tetrahydrofuran
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CN108993487A (en
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丁辉
郝子全
王路路
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Tianjin University
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • 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 discloses the method for preparing catalyst that nitrogen and hydrogen generation ammonia are catalyzed under a kind of room temperature, comprising the following steps: (1) prepares trimethyl platinum diiodide and trimethyl iodate ruthenium using lithium methide the preparation method；(2) hexamethyl-methyl cyclopentadiene closes the preparation of platinum ruthenium；(3) technique for atomic layer deposition prepares Ru-Pt/TiO2Monatomic catalyst.Compared with existing catalyst, present invention has an advantage that catalyst Ru-Pt/TiO2High-efficient, the service life is long, has stronger anti-poisoning capability, greatly reduces reaction activity, catalytic efficiency is significantly promoted；TiO2As carrier, there is polymolecularity, the advantage of high porosity；Using the monatomic catalyst of bimetallic, synergistic effect is had between metal and metal, promotes to catalyze and synthesize ammonia reaction together.

Description

It is catalyzed nitrogen under a kind of room temperature and hydrogen generates the method for preparing catalyst of ammonia
Technical field
The present invention relates to the catalyst systems that method for preparing catalyst more particularly to a kind of catalysis nitrogen and hydrogen generate ammonia Preparation Method.
Background technique
Ammonia is important one of inorganic chemical product, occupies an important position in national economy.Except liquefied ammonia can be directly as Outside fertilizer, the nitrogenous fertilizer agriculturally used, such as urea, ammonium nitrate, ammonium phosphate, ammonium chloride and it is various contain nitrogen composite fertilizer, be all Using ammonia as raw material.The world synthesizes hydrazine yield up to 100,000,000 tons or more every year, wherein there are about 80% ammonia to be used to produce chemical fertilizer Material, 20% raw material as other chemical products.
It is well known that German chemist Haber began one's study from 1902 directly synthesizes ammonia with nitrogen and hydrogen, in 1908 Year applies for a patent, i.e. round-robin method, and on this basis, he continues to study, and synthesis was improved in 1909, and the content of ammonia reaches 6% More than, this is the direct synthesis technique that industry generallys use.Calculation of thermodynamics shows that cryogenic high pressure is advantageous to ammonia synthesis reaction , but when without catalyst, the activation energy of reaction is very high, and reaction hardly happens.It is anti-due to changing when using iron catalyst Course is answered, the activation energy of reaction is reduced, makes reaction with the progress of significant rate.The mechanism of ammonia synthesis reaction is nitrogen point first Son chemisorption on iron catalyst surface weakens the chemical bond between nitrogen-atoms, then the hydrogen atom of chemisorption constantly with Nitrogen molecular effect on surface, last nitrogen molecular is desorbed on catalyst surface generates gaseous ammonia.
Catalyst is destroyed activity decline even during stabilizing active, this existing As referred to as catalyst poisoning.For the iron catalyst in ammonia synthesis reaction, O2、CO、CO2It can make in catalyst with vapor etc. Poison.But when passing through fouled catalyst using pure hydrogen, nitrogen mixture gas, the activity of catalyst can be restored again, therefore this Poisoning is temporary poisoning.On the contrary, the compound containing P, S, As then can make iron catalyst permanently be poisoned.After catalyst poisoning, Often lose activity completely, even if at this moment again with pure hydrogen, nitrogen mixture gas processing, it is active to be also difficult to restore.In catalyst Poison can seriously affect being normally carried out for production, industrially catalyst poisoning in order to prevent, and reactant feed is purified, with Poisonous substance is removed, equipment is thus increased, improves cost.Therefore, the new catalyst with stronger poison resistance is developed, is one A important project.
Synthetic ammonia catalyst has been subjected to the development course in a century, quite mature.But traditional fused iron catalyst The development trend of low energy consumption is not met, and ruthenium-base alloy ammonification catalyst is expensive, is not easy to popularize.In nearest research, have Scholar report it is a kind of it is nano-material modified after ammonia synthesis catalyst, can be improved 15% or more catalyst activity, improve and turn 30% or more rate, and reaction temperature is lower, but also not fully up to expectations in terms of selectivity.Monatomic catalyst (SACs) refers to Metal is dispersed in the catalyst with excellent catalytic performance formed on carrier with monatomic form, urges with conventional carriers type Agent is compared, SACs it is active it is high, selectivity it is good, noble metal utilisation is high the advantages that, oxidation reaction, Water gas shift/WGS, The fields such as hydrogenation reaction and electrochemical catalysis are all widely used.Experiment and theoretical research show that monatomic catalyst is high Activity and selectivity is attributable to the interaction between active metal atom and carrier and thus caused electronic structure changes Become.
Summary of the invention
The purpose of the present invention is to overcome the disadvantages of the prior art, provides a kind of catalysis nitrogen and hydrogen generates ammonia and urges Agent preparation method, this method can prepare catalyst at normal temperature, have with monatomic catalyst prepared by this method relatively strong anti- Malicious ability, the ammonia synthesis reaction temperature carried out with the monatomic catalyst is low, greatly reduces reaction activity, and catalytic efficiency is big Amplitude is promoted.
The technical scheme is that
It is catalyzed nitrogen under a kind of room temperature of the invention and hydrogen generates the method for preparing catalyst of ammonia, including following step It is rapid:
Step 1: preparation hexamethyl-methyl cyclopentadiene closes platinum ruthenium:
(a) trimethyl platinum diiodide and trimethyl iodate ruthenium are prepared using lithium methide the preparation method respectively in oxygen-free environment:
(1) in anhydrous and oxygen-free environment, at a temperature of -30 DEG C -0 DEG C, K is weighed2PtCl6It is placed in four-hole boiling flask, is put into magnetic The stirring of power stirrer, is then placed in low-temp reaction kettle, and adjustment temperature is -20 DEG C -0 DEG C, and flask is added after extracting tetrahydrofuran In, to K2PtCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.5-1.8mol/L lithium methide is slowly added dropwise, later 12-16h is reacted, PtMe is obtained3Cl mixed liquor, the K2PtCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution rub You are than being 1:(2-3): (8-9)；
In anhydrous and oxygen-free environment, at a temperature of -30 DEG C -0 DEG C, K is weighed2RuCl6It is placed in four-hole boiling flask, and is put into magnetic The stirring of power stirrer, is then placed in low-temp reaction kettle, and adjustment temperature is -20 DEG C -0 DEG C, and flask is added after extracting tetrahydrofuran In, to K2RuCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.5-1.8mol/L lithium methide is slowly added dropwise, later 12-16h is reacted, RuMe is obtained3Cl mixed liquor, the K2RuCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution rub You are than being 1:(2-3): (8-9)；
(2) at -20 DEG C -0 DEG C, excessive 1,2- Bromofume is separately added into the PtMe3Cl mixed liquor, RuMe3In Cl mixed liquor, then respectively in PtMe3Cl mixed liquor, RuMe3The hydrochloric acid of 0.8-1.2mol/L KI is added in Cl mixed liquor Saturated solution, the PtMe3Cl mixed liquor and the hydrochloric acid saturated solution volume ratio of KI, RuMe3The hydrochloric acid of Cl mixed liquor and KI are full With liquor capacity ratio respectively 3:(1-2), 3:(1-2), reaction generates precipitating, precipitates and does not take out, and being eventually adding can be complete molten The deionized water for solving precipitating, warms naturally to 10-40 DEG C；
(3) it is separately added into two kinds of precipitating lysates obtained in (b) using ether as extractant, extracts organic phase, Solvent evaporated, is added acetone washing, and filtering obtains trimethyl platinum diiodide and trimethyl iodate ruthenium solid；
(b) it prepares hexamethyl-methyl cyclopentadiene and closes platinum ruthenium:
(1) in anhydrous and oxygen-free environment, at a temperature of -10~50 DEG C using trimethyl platinum diiodide and trimethyl iodate ruthenium as Raw material is mixed with the tetrahydrofuran of water removal, the trimethyl platinum diiodide, trimethyl iodate ruthenium and the tetrahydrofuran quality of water removal Than for 1:1:(2-3)；
(2) the methyl ring penta 2 that quality is 2-2.6 times of trimethyl platinum diiodide is added in the mixture of step (1) in (b) Alkenyl disodium reacts 0.9-1.1h, deionized water is added later, uses pentane as extractant, extracts organic phase, be evaporated it In solvent, using sublimator under negative pressure condition, sublimation purification obtains product hexamethyl-methyl ring in 70-80 DEG C of water-bath Pentadiene closes platinum ruthenium；Step 2: preparation Ru-Pt/TiO2Monatomic catalyst:
(a) atomic layer deposition method is used, platinum ruthenium and oxygen are closed as before deposition reaction using hexamethyl-methyl cyclopentadiene Body is driven, is 150-200m by specific surface area2The TiO that/g and quality are 10-15g2High temperature resistant quartz glass plate is placed on as carrier On, TiO is made as dispersion liquid for the ethyl alcohol of 98-99% using mass fraction2It is dispersed on quartz glass plate, it is direct after dry Quartz glass plate is put into atomic layer deposition reaction cavity；
(b) heat presoma hexamethyl-methyl cyclopentadiene and close platinum ruthenium to 50-60 DEG C, then make its with impulse form into Enter reaction chamber, start deposition reaction when quartz glass plate reaches 150-300 DEG C in reaction chamber, to an atomic layer deposition cycles according to Secondary includes that 20-25s hexamethyl-methyl cyclopentadiene closes the pulse of platinum ruthenium, 10-12s exposure duration, 95-105s N2Purging, 40- 45s pulse of oxygen, 10-12s exposure duration, 95-105s N2It purges, N in deposition process2Flow is 120-180mL/min, according to Need to change the cycle-index of deposition, to obtain the Ru-Pt/TiO of different platinum ruthenium contents2Monatomic catalyst.
Present invention has an advantage that catalyst Ru-Pt/TiO2High-efficient, the service life is long, and monatomic catalyst has stronger anti- Poisoning capability has very big advantage in ammonia synthesis reaction；TiO2As carrier, except having, nontoxic, performance is stable, price is low Outside the advantages that honest and clean, anticorrosive, also as aluminium oxide, there are polymolecularity, high porosity；Using the monatomic catalyst of bimetallic, Synergistic effect is had between metal and metal, promotes to catalyze and synthesize ammonia reaction together, in bimetallic catalyst Ru-Pt/TiO2In, Due to the difference of electronegativity between Ru and Pt, cause the electronics of delocalization be not it is equally distributed, the presence of Pt can be mentioned significantly Activity of the high Ru in catalysis reaction.
Specific embodiment
Below in conjunction with case study on implementation of the present invention, the technical solution in case study on implementation of the present invention is carried out clear, complete Description, it is clear that described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.Based on this The embodiment of invention, every other implementation obtained by those of ordinary skill in the art without making creative efforts Example, shall fall within the protection scope of the present invention.
Of the invention the reaction mechanism is as follows: having evenly dispersed monatomic ruthenium and platinum in supported on carriers, due to two kinds of lists Atom derives from same presoma, and ruthenium and platinum occupy adjacent site respectively when preparation.When ammonia synthesis reaction carries out, nitrogen point Son and hydrogen molecule are attracted by adjacent ruthenium and platinum is monatomic respectively, and chemisorption occurs for surface so that between nitrogen-atoms with And chemical bond weakens between hydrogen atom, then adjacent nitrogen-atoms and hydrogen atom effect carries out series reaction in catalyst surface, Ultimately produce gaseous ammonia.
It is catalyzed nitrogen based on the above mechanism, under a kind of room temperature of the invention and hydrogen generates the catalyst preparation side of ammonia Method, comprising the following steps:
Step 1: preparation hexamethyl-methyl cyclopentadiene closes platinum ruthenium:
(a) trimethyl platinum diiodide and trimethyl iodate ruthenium are prepared using lithium methide the preparation method respectively in oxygen-free environment:
(1) in anhydrous and oxygen-free environment, at a temperature of -30 DEG C -0 DEG C, K is weighed2PtCl6It is placed in four-hole boiling flask, is put into magnetic The stirring of power stirrer, is then placed in low-temp reaction kettle, and adjustment temperature is -20 DEG C -0 DEG C, and flask is added after extracting tetrahydrofuran In, to K2PtCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.5-1.8mol/L lithium methide is slowly added dropwise, later 12-16h is reacted, PtMe is obtained3Cl mixed liquor, the K2PtCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution rub You are than being 1:(2-3): (8-9)；
In anhydrous and oxygen-free environment, at a temperature of -30 DEG C -0 DEG C, K is weighed2RuCl6It is placed in four-hole boiling flask, and is put into magnetic The stirring of power stirrer, is then placed in low-temp reaction kettle, and adjustment temperature is -20 DEG C -0 DEG C, and flask is added after extracting tetrahydrofuran In, to K2RuCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.5-1.8mol/L lithium methide is slowly added dropwise, later 12-16h is reacted, RuMe is obtained3Cl mixed liquor, the K2RuCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution rub You are than being 1:(2-3): (8-9)；
(2) at -20 DEG C -0 DEG C, excessive 1,2- Bromofume is separately added into the PtMe3Cl mixed liquor, RuMe3In Cl mixed liquor, then respectively in PtMe3Cl mixed liquor, RuMe3The hydrochloric acid of 0.8-1.2mol/L KI is added in Cl mixed liquor Saturated solution, the PtMe3Cl mixed liquor and the hydrochloric acid saturated solution volume ratio of KI, RuMe3The hydrochloric acid of Cl mixed liquor and KI are full With liquor capacity ratio respectively 3:(1-2), 3:(1-2), reaction generates precipitating, precipitates and does not take out, and being eventually adding can be complete molten The deionized water for solving precipitating, warms naturally to 10-40 DEG C；
(3) it is separately added into two kinds of precipitating lysates obtained in (2) using ether as extractant, extracts organic phase, Solvent evaporated, is added acetone washing, and filtering obtains trimethyl platinum diiodide and trimethyl iodate ruthenium solid；
(b) it prepares hexamethyl-methyl cyclopentadiene and closes platinum ruthenium:
(1) in anhydrous and oxygen-free environment, at a temperature of -10~50 DEG C using trimethyl platinum diiodide and trimethyl iodate ruthenium as Raw material is mixed with the tetrahydrofuran of water removal, the trimethyl platinum diiodide, trimethyl iodate ruthenium and the tetrahydrofuran quality of water removal Than for 1:1:(2-3)；
(2) the methyl ring penta 2 that quality is 2-2.6 times of trimethyl platinum diiodide is added in the mixture of step (1) in (b) Alkenyl disodium reacts 0.9-1.1h, deionized water is added later, uses pentane as extractant, extracts organic phase, be evaporated it In solvent, using sublimator under negative pressure (lower than the gas pressure state of an atmospheric pressure) situation, in 70-80 DEG C of water-bath Sublimation purification obtains product hexamethyl-methyl cyclopentadiene and closes platinum ruthenium；
Step 2: preparation Ru-Pt/TiO2Monatomic catalyst:
(a) atomic layer deposition method is used, platinum ruthenium (MeCpPtRuMe is closed with hexamethyl-methyl cyclopentadiene6) and oxygen work It is 150-200m by specific surface area for the presoma of deposition reaction2The TiO that/g and quality are 10-15g2Resistance to height is placed on as carrier On warm quartz glass plate, TiO is made as dispersion liquid for the ethyl alcohol of 98-99% using mass fraction2It is dispersed in quartz glass plate On, directly quartz glass plate is put into atomic layer deposition reaction cavity after dry；
(b) heat presoma hexamethyl-methyl cyclopentadiene and close platinum ruthenium to 50-60 DEG C, then make its with impulse form into Enter reaction chamber, starts deposition reaction when quartz glass plate reaches 150-300 DEG C in reaction chamber, an atomic layer deposition cycles are successively The pulse of platinum ruthenium, 10-12s exposure duration, 95-105s N are closed including 20-25s hexamethyl-methyl cyclopentadiene2Purging, 40-45s Pulse of oxygen, 10-12s exposure duration, 95-105s N2Purging.N in deposition process2Flow is 120-180mL/min, according to need Change the cycle-index of deposition, to obtain the Ru-Pt/TiO of different platinum ruthenium contents2Monatomic catalyst.Cycle-index is more, Then Ru-Pt/TiO2Platinum ruthenium load capacity is higher in monatomic catalyst, catalytic activity enhancing, but when cycle-index is excessive, load Platinum ruthenium can also block TiO2Duct, catalytic activity reduce.
Embodiment 1
Step 1: preparation hexamethyl-methyl cyclopentadiene closes platinum ruthenium:
(a) trimethyl platinum diiodide and trimethyl iodate ruthenium are prepared using lithium methide the preparation method respectively in oxygen-free environment:
(1) in anhydrous and oxygen-free environment, at a temperature of -30 DEG C, 0.2molK is weighed2PtCl6It is placed in four-hole boiling flask, is put into Magnetic stir bar stirring, is then placed in low-temp reaction kettle, and adjustment temperature is -20 DEG C, is added in flask after extracting tetrahydrofuran, To K2PtCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.5mol/L lithium methide is slowly added dropwise, reacts later 12h obtains PtMe3Cl mixed liquor, the K2PtCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution molar ratio be 1: 2:8；
In anhydrous and oxygen-free environment, at a temperature of -30 DEG C, 0.2molK is weighed2RuCl6It is placed in four-hole boiling flask, and is put into Magnetic stir bar stirring, is then placed in low-temp reaction kettle, and adjustment temperature is -20 DEG C, is added in flask after extracting tetrahydrofuran, To K2RuCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.5mol/L lithium methide is slowly added dropwise, reacts later 12h obtains RuMe3Cl mixed liquor, the K2RuCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution molar ratio be 1: 2:8；
(2) at -20 DEG C, by 20mL1,2- Bromofume is separately added into the PtMe3Cl mixed liquor, RuMe3Cl mixing In liquid, then respectively in PtMe3Cl mixed liquor, RuMe3The hydrochloric acid saturated solution of 10mL0.8mol/L KI, institute are added in Cl mixed liquor The PtMe stated3Cl mixed liquor and the hydrochloric acid saturated solution volume ratio of KI, RuMe3The hydrochloric acid saturated solution volume of Cl mixed liquor and KI Than being respectively 3:1,3:1, reaction, which generates, to be precipitated, and precipitating is not taken out, and is eventually adding the deionized water that can be completely dissolved precipitating, from So it is warming up to 10 DEG C；
(3) it is separately added into two kinds of precipitating lysates obtained in (2) using ether as extractant, extracts organic phase, Solvent evaporated, is added acetone washing, and filtering obtains trimethyl platinum diiodide and trimethyl iodate ruthenium solid；
(b) it prepares hexamethyl-methyl cyclopentadiene and closes platinum ruthenium:
(1) in anhydrous and oxygen-free environment, at a temperature of -10 DEG C using 5g trimethyl platinum diiodide and 5g trimethyl iodate ruthenium as Raw material is mixed with the tetrahydrofuran of water removal, the trimethyl platinum diiodide, trimethyl iodate ruthenium and the tetrahydrofuran quality of water removal Than for 1:1:2；
(2) methyl cyclopentadienyl that quality is 2 times of trimethyl platinum diiodide is added in the mixture of step (1) in (b) Disodium reacts 0.9h, deionized water is added later, uses pentane as extractant, extracts organic phase, be evaporated therein molten Agent, using sublimator under 50kPa situation, sublimation purification obtains product hexamethyl-methyl cyclopentadiene conjunction in 70 DEG C of water-baths Platinum ruthenium；
Step 2: preparation Ru-Pt/TiO2Monatomic catalyst:
(a) atomic layer deposition method is used, platinum ruthenium (MeCpPtRuMe is closed with hexamethyl-methyl cyclopentadiene6) and oxygen work It is 150m by specific surface area for the presoma of deposition reaction2The TiO that/g and quality are 10g2High temperature resistant quartz is placed on as carrier On glass plate, TiO is made as dispersion liquid using the ethyl alcohol that mass fraction is 98%2It is dispersed on quartz glass plate, after dry Directly quartz glass plate is put into atomic layer deposition reaction cavity；
(b) it heats presoma hexamethyl-methyl cyclopentadiene and closes platinum ruthenium to 50 DEG C, enter it with impulse form anti- Chamber is answered, starts deposition reaction when quartz glass plate reaches 150 DEG C in reaction chamber, an atomic layer deposition cycles successively include 20s Hexamethyl-methyl cyclopentadiene closes the pulse of platinum ruthenium, 10s exposure duration, 95s N2Purging, 40s pulse of oxygen, 10s exposure duration, 95s N2Purging.N in deposition process2Flow is 120mL/min, obtains Ru-Pt/TiO deposition cycle 3 times2Monatomic catalyst.
The evaluation of catalyst ammonia synthesizing activity carries out in ammonia synthesis high pressure reaction assembly, and the present embodiment is packed into reactor Catalyst 2mL to be measured obtained, then N is passed through to reaction system2With H2Volume ratio is the reaction gas of 1:1, and concentrations of reactant gas is 1000mg/m3, air speed 7500h-1, with gas chromatographic detection import concentrations of reactant gas, outlet reaction is measured with chemical absorption method Ammonia density in gas.The catalytic performance of monatomic catalyst, is shown in Table 1.
Embodiment 2
Step 1: preparation hexamethyl-methyl cyclopentadiene closes platinum ruthenium:
(a) trimethyl platinum diiodide and trimethyl iodate ruthenium are prepared using lithium methide the preparation method respectively in oxygen-free environment:
(1) in anhydrous and oxygen-free environment, at a temperature of -15 DEG C, 0.2molK is weighed2PtCl6It is placed in four-hole boiling flask, is put into Magnetic stir bar stirring, is then placed in low-temp reaction kettle, and adjustment temperature is -10 DEG C, is added in flask after extracting tetrahydrofuran, To K2PtCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.6mol/L lithium methide is slowly added dropwise, reacts later 14h obtains PtMe3Cl mixed liquor, the K2PtCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution molar ratio be 1: 2.5:8.5；
In anhydrous and oxygen-free environment, at a temperature of -15 DEG C, 0.2mol K is weighed2RuCl6It is placed in four-hole boiling flask, and is put into Magnetic stir bar stirring, is then placed in low-temp reaction kettle, and adjustment temperature is -10 DEG C, is added in flask after extracting tetrahydrofuran, To K2RuCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.6mol/L lithium methide is slowly added dropwise, reacts later 14h obtains RuMe3Cl mixed liquor, the K2RuCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution molar ratio be 1: 2.5:8.5；
(2) at -10 DEG C, by 20mL 1,2- Bromofume is separately added into the PtMe3Cl mixed liquor, RuMe3Cl is mixed It closes in liquid, then respectively in PtMe3Cl mixed liquor, RuMe3The hydrochloric acid saturated solution of 10mL1mol/L KI, institute are added in Cl mixed liquor The PtMe stated3Cl mixed liquor and the hydrochloric acid saturated solution volume ratio of KI, RuMe3The hydrochloric acid saturated solution volume of Cl mixed liquor and KI Than being respectively 2:1,2:1, reaction, which generates, to be precipitated, and precipitating is not taken out, and is eventually adding the deionized water that can be completely dissolved precipitating, from So it is warming up to 25 DEG C；
(3) it is separately added into two kinds of precipitating lysates obtained in (2) using ether as extractant, extracts organic phase, Solvent evaporated, is added acetone washing, and filtering obtains trimethyl platinum diiodide and trimethyl iodate ruthenium solid；
(b) it prepares hexamethyl-methyl cyclopentadiene and closes platinum ruthenium:
(1) in anhydrous and oxygen-free environment, at a temperature of 20 DEG C using 5g trimethyl platinum diiodide and 5g trimethyl iodate ruthenium as Raw material is mixed with the tetrahydrofuran of water removal, the trimethyl platinum diiodide, trimethyl iodate ruthenium and the tetrahydrofuran quality of water removal Than for 1:1:2.5；
(2) methyl cyclopentadiene that quality is 2.4 times of trimethyl platinum diiodide is added in the mixture of step (1) in (b) Base disodium reacts 1h, deionized water is added later, uses pentane as extractant, extracts organic phase, be evaporated therein molten Agent, using sublimator under 50kPa situation, sublimation purification obtains product hexamethyl-methyl cyclopentadiene conjunction in 75 DEG C of water-baths Platinum ruthenium；
Step 2: preparation Ru-Pt/TiO2Monatomic catalyst:
(a) atomic layer deposition method is used, platinum ruthenium (MeCpPtRuMe is closed with hexamethyl-methyl cyclopentadiene6) and oxygen work It is 175m by specific surface area for the presoma of deposition reaction2The TiO that/g and quality are 12g2High temperature resistant quartz is placed on as carrier On glass plate, TiO is made as dispersion liquid using the ethyl alcohol that mass fraction is 98.5%2It is dispersed on quartz glass plate, it is dry Directly quartz glass plate is put into atomic layer deposition reaction cavity afterwards；
(b) it heats presoma hexamethyl-methyl cyclopentadiene and closes platinum ruthenium to 55 DEG C, enter it with impulse form anti- Chamber is answered, starts deposition reaction when quartz glass plate reaches 225 DEG C in reaction chamber, an atomic layer deposition cycles successively include 22s Hexamethyl-methyl cyclopentadiene closes the pulse of platinum ruthenium, 11s exposure duration, 100s N2When purging, 42s pulse of oxygen, 11s exposure Between, 100s N2Purging.N in deposition process2Flow is 150mL/min, obtains Ru-Pt/TiO deposition cycle 3 times2Monatomic catalysis Agent.
The evaluation of catalyst ammonia synthesizing activity carries out in ammonia synthesis high pressure reaction assembly, and the present embodiment is packed into reactor Catalyst 2mL to be measured obtained, then N is passed through to reaction system2With H2Volume ratio is the reaction gas of 1:1, and concentrations of reactant gas is 1000mg/m3, air speed 7500h-1, with gas chromatographic detection import concentrations of reactant gas, outlet reaction is measured with chemical absorption method Ammonia density in gas.The catalytic performance of monatomic catalyst, is shown in Table 1.
Embodiment 3
Step 1: preparation hexamethyl-methyl cyclopentadiene closes platinum ruthenium:
(a) trimethyl platinum diiodide and trimethyl iodate ruthenium are prepared using lithium methide the preparation method respectively in oxygen-free environment:
(1) in anhydrous and oxygen-free environment, at a temperature of -10 DEG C, 0.2mol K is weighed2PtCl6It is placed in four-hole boiling flask, puts Enter magnetic stir bar stirring, be then placed in low-temp reaction kettle, adjustment temperature is -10 DEG C, and flask is added after extracting tetrahydrofuran In, to K2PtCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.7mol/L lithium methide is slowly added dropwise, reacts later 14h obtains PtMe3Cl mixed liquor, the K2PtCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution molar ratio be 1: 2.5:8.5；
In anhydrous and oxygen-free environment, at a temperature of -10 DEG C, 0.2mol K is weighed2RuCl6It is placed in four-hole boiling flask, and is put into Magnetic stir bar stirring, is then placed in low-temp reaction kettle, and adjustment temperature is -10 DEG C, is added in flask after extracting tetrahydrofuran, To K2RuCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.7mol/L lithium methide is slowly added dropwise, reacts later 14h obtains RuMe3Cl mixed liquor, the K2RuCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution molar ratio be 1: 2.5:8.5；
(2) at -10 DEG C, by 20mL 1,2- Bromofume is separately added into the PtMe3Cl mixed liquor, RuMe3Cl is mixed It closes in liquid, then respectively in PtMe3Cl mixed liquor, RuMe3The hydrochloric acid saturated solution of 10mL1mol/L KI, institute are added in Cl mixed liquor The PtMe stated3Cl mixed liquor and the hydrochloric acid saturated solution volume ratio of KI, RuMe3The hydrochloric acid saturated solution volume of Cl mixed liquor and KI Than being respectively 2:1,2:1, reaction, which generates, to be precipitated, and precipitating is not taken out, and is eventually adding the deionized water that can be completely dissolved precipitating, from So it is warming up to 25 DEG C；
(3) it is separately added into two kinds of precipitating lysates obtained in (2) using ether as extractant, extracts organic phase, Solvent evaporated, is added acetone washing, and filtering obtains trimethyl platinum diiodide and trimethyl iodate ruthenium solid；
(b) it prepares hexamethyl-methyl cyclopentadiene and closes platinum ruthenium:
(1) in anhydrous and oxygen-free environment, at a temperature of 20 DEG C using 5g trimethyl platinum diiodide and 5g trimethyl iodate ruthenium as Raw material is mixed with the tetrahydrofuran of water removal, the trimethyl platinum diiodide, trimethyl iodate ruthenium and the tetrahydrofuran quality of water removal Than for 1:1:2.5；
(2) methyl cyclopentadiene that quality is 2.2 times of trimethyl platinum diiodide is added in the mixture of step (1) in (b) Base disodium reacts 1h, deionized water is added later, uses pentane as extractant, extracts organic phase, be evaporated therein molten Agent, using sublimator under 50kPa situation, sublimation purification obtains product hexamethyl-methyl cyclopentadiene conjunction in 75 DEG C of water-baths Platinum ruthenium；
Step 2: preparation Ru-Pt/TiO2Monatomic catalyst:
(a) atomic layer deposition method is used, platinum ruthenium (MeCpPtRuMe is closed with hexamethyl-methyl cyclopentadiene6) and oxygen work It is 175m by specific surface area for the presoma of deposition reaction2The TiO that/g and quality are 12g2High temperature resistant quartz is placed on as carrier On glass plate, TiO is made as dispersion liquid using the ethyl alcohol that mass fraction is 99%2It is dispersed on quartz glass plate, after dry Directly quartz glass plate is put into atomic layer deposition reaction cavity；
(b) it heats presoma hexamethyl-methyl cyclopentadiene and closes platinum ruthenium to 55 DEG C, enter it with impulse form anti- Chamber is answered, starts deposition reaction when quartz glass plate reaches 225 DEG C in reaction chamber, an atomic layer deposition cycles successively include 22s Hexamethyl-methyl cyclopentadiene closes the pulse of platinum ruthenium, 11s exposure duration, 100s N2When purging, 44s pulse of oxygen, 11s exposure Between, 100s N2Purging.N in deposition process2Flow is 160mL/min, obtains Ru-Pt/TiO deposition cycle 3 times2Monatomic catalysis Agent.
The evaluation of catalyst ammonia synthesizing activity carries out in ammonia synthesis high pressure reaction assembly, and the present embodiment is packed into reactor Catalyst 2mL to be measured obtained, then N is passed through to reaction system2With H2Volume ratio is the reaction gas of 1:1, and concentrations of reactant gas is 1000mg/m3, air speed 7500h-1, with gas chromatographic detection import concentrations of reactant gas, outlet reaction is measured with chemical absorption method Ammonia density in gas.The catalytic performance of monatomic catalyst, is shown in Table 1.
Embodiment 4
Step 1: preparation hexamethyl-methyl cyclopentadiene closes platinum ruthenium:
(a) trimethyl platinum diiodide and trimethyl iodate ruthenium are prepared using lithium methide the preparation method respectively in oxygen-free environment:
(1) in anhydrous and oxygen-free environment, at a temperature of 0 DEG C, 0.2mol K is weighed2PtCl6It is placed in four-hole boiling flask, is put into Magnetic stir bar stirring, is then placed in low-temp reaction kettle, and adjustment temperature is 0 DEG C, is added in flask after extracting tetrahydrofuran, to K2PtCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.8mol/L lithium methide is slowly added dropwise, reacts 16h later, Obtain PtMe3Cl mixed liquor, the K2PtCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution molar ratio be 1:3:9；
In anhydrous and oxygen-free environment, at a temperature of 0 DEG C, 0.2mol K is weighed2RuCl6It is placed in four-hole boiling flask, and is put into magnetic The stirring of power stirrer, is then placed in low-temp reaction kettle, and adjustment temperature is 0 DEG C, is added in flask after extracting tetrahydrofuran, to K2RuCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.8mol/L lithium methide is slowly added dropwise, reacts 16h later, Obtain RuMe3Cl mixed liquor, the K2RuCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution molar ratio be 1:3:9；
(2) at 0 DEG C, by 20mL 1,2- Bromofume is separately added into the PtMe3Cl mixed liquor, RuMe3Cl mixing In liquid, then respectively in PtMe3Cl mixed liquor, RuMe3The hydrochloric acid saturated solution of 10mL1.2mol/L KI, institute are added in Cl mixed liquor The PtMe stated3Cl mixed liquor and the hydrochloric acid saturated solution volume ratio of KI, RuMe3The hydrochloric acid saturated solution volume of Cl mixed liquor and KI Than being respectively 3:2,3:2, reaction, which generates, to be precipitated, and precipitating is not taken out, and is eventually adding the deionized water that can be completely dissolved precipitating, from So it is warming up to 40 DEG C；
(3) it is separately added into two kinds of precipitating lysates obtained in (2) using ether as extractant, extracts organic phase, Solvent evaporated, is added acetone washing, and filtering obtains trimethyl platinum diiodide and trimethyl iodate ruthenium solid；
(b) it prepares hexamethyl-methyl cyclopentadiene and closes platinum ruthenium:
(1) in anhydrous and oxygen-free environment, at 50 °C using 5g trimethyl platinum diiodide and 5g trimethyl iodate ruthenium as Raw material is mixed with the tetrahydrofuran of water removal, the trimethyl platinum diiodide, trimethyl iodate ruthenium and the tetrahydrofuran quality of water removal Than for 1:1:3；
(2) methyl cyclopentadiene that quality is 2.6 times of trimethyl platinum diiodide is added in the mixture of step (1) in (b) Base disodium reacts 1.1h, deionized water is added later, uses pentane as extractant, extracts organic phase, be evaporated therein molten Agent, using sublimator under 50kPa situation, sublimation purification obtains product hexamethyl-methyl cyclopentadiene conjunction in 80 DEG C of water-baths Platinum ruthenium；
Step 2: preparation Ru-Pt/TiO2Monatomic catalyst:
(a) atomic layer deposition method is used, platinum ruthenium (MeCpPtRuMe is closed with hexamethyl-methyl cyclopentadiene6) and oxygen work It is 200m by specific surface area for the presoma of deposition reaction2The TiO that/g and quality are 15g2High temperature resistant quartz is placed on as carrier On glass plate, TiO is made as dispersion liquid using the ethyl alcohol that mass fraction is 99%2It is dispersed on quartz glass plate, after dry Directly quartz glass plate is put into atomic layer deposition reaction cavity；
(b) it heats presoma hexamethyl-methyl cyclopentadiene and closes platinum ruthenium to 60 DEG C, enter it with impulse form anti- Chamber is answered, starts deposition reaction when quartz glass plate reaches 300 DEG C in reaction chamber, an atomic layer deposition cycles successively include 25s Hexamethyl-methyl cyclopentadiene closes the pulse of platinum ruthenium, 12s exposure duration, 105s N2When purging, 45s pulse of oxygen, 12s exposure Between, 105s N2Purging.N in deposition process2Flow is 180mL/min, obtains Ru-Pt/TiO deposition cycle 3 times2Monatomic catalysis Agent.
The evaluation of catalyst ammonia synthesizing activity carries out in ammonia synthesis high pressure reaction assembly, and the present embodiment is packed into reactor Catalyst 2mL to be measured obtained, then N is passed through to reaction system2With H2Volume ratio is the reaction gas of 1:1, and concentrations of reactant gas is 1000mg/m3, air speed 7500h-1, with gas chromatographic detection import concentrations of reactant gas, outlet reaction is measured with chemical absorption method Ammonia density in gas.The catalytic performance of monatomic catalyst, is shown in Table 1.
1 Ru-Pt/TiO of table2Ammonia synthesis catalytic perfomance on monatomic catalyst
Figure GDA0002127719940000141

Claims (1)

1. being catalyzed nitrogen under a kind of room temperature and hydrogen generating the method for preparing catalyst of ammonia, comprising the following steps:
Step 1: preparation hexamethyl-methyl cyclopentadiene closes platinum ruthenium:
(a) trimethyl platinum diiodide and trimethyl iodate ruthenium are prepared using lithium methide the preparation method respectively in oxygen-free environment:
(1) in anhydrous and oxygen-free environment, at a temperature of -30 DEG C -0 DEG C, K is weighed2PtCl6It is placed in four-hole boiling flask, is put into magnetic force and stirs Sub- stirring to be mixed, is then placed in low-temp reaction kettle, adjustment temperature is -20 DEG C -0 DEG C, it is added in flask after extracting tetrahydrofuran, to K2PtCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.5-1.8mol/L lithium methide is slowly added dropwise, reacts later 12-16h obtains PtMe3Cl mixed liquor, the K2PtCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution molar ratio For 1:(2-3): (8-9)；
In anhydrous and oxygen-free environment, at a temperature of -30 DEG C -0 DEG C, K is weighed2RuCl6It is placed in four-hole boiling flask, and is put into magnetic force and stirs Sub- stirring to be mixed, is then placed in low-temp reaction kettle, adjustment temperature is -20 DEG C -0 DEG C, it is added in flask after extracting tetrahydrofuran, to K2RuCl6In the mixture of water removal tetrahydrofuran, the diethyl ether solution of 1.5-1.8mol/L lithium methide is slowly added dropwise, reacts later 12-16h obtains RuMe3Cl mixed liquor, the K2RuCl6, water removal tetrahydrofuran and lithium methide diethyl ether solution molar ratio For 1:(2-3): (8-9)；
(2) at -20 DEG C -0 DEG C, excessive 1,2- Bromofume is separately added into the PtMe3Cl mixed liquor, RuMe3Cl is mixed It closes in liquid, then respectively in PtMe3Cl mixed liquor, RuMe3The hydrochloric acid saturated solution of 0.8-1.2mol/L KI is added in Cl mixed liquor, The PtMe3Cl mixed liquor and the hydrochloric acid saturated solution volume ratio of KI, RuMe3The hydrochloric acid saturated solution body of Cl mixed liquor and KI Product than be respectively 3:(1-2), 3:(1-2), reaction generate precipitating, precipitating do not take out, precipitating can be completely dissolved by being eventually adding Deionized water warms naturally to 10-40 DEG C；
(3) it is separately added into two kinds of precipitating lysates obtained in (2) using ether as extractant, extracts organic phase, be evaporated Solvent, is added acetone washing, and filtering obtains trimethyl platinum diiodide and trimethyl iodate ruthenium solid；
(b) it prepares hexamethyl-methyl cyclopentadiene and closes platinum ruthenium:
(1) in anhydrous and oxygen-free environment, using trimethyl platinum diiodide and trimethyl iodate ruthenium as original at a temperature of -10~50 DEG C Material, mixes, the trimethyl platinum diiodide, trimethyl iodate ruthenium and the tetrahydrofuran mass ratio of water removal with the tetrahydrofuran of water removal For 1:1:(2-3)；
(2) methyl cyclopentadienyl that quality is 2-2.6 times of trimethyl platinum diiodide is added in the mixture of step (1) in (b) Disodium reacts 0.9-1.1h, deionized water is added later, uses pentane as extractant, extracts organic phase, be evaporated therein Solvent, using sublimator under negative pressure condition, sublimation purification obtains product hexamethyl-methyl ring penta 2 in 70-80 DEG C of water-bath Alkene closes platinum ruthenium；
Step 2: preparation Ru-Pt/TiO2Monatomic catalyst:
(a) atomic layer deposition method is used, platinum ruthenium and oxygen are closed as the forerunner of deposition reaction using hexamethyl-methyl cyclopentadiene Specific surface area is 150-200m by body2The TiO that/g and quality are 10-15g2It is placed on high temperature resistant quartz glass plate as carrier, Make TiO as dispersion liquid for the ethyl alcohol of 98-99% using mass fraction2It is dispersed on quartz glass plate, directly will after dry Quartz glass plate is put into atomic layer deposition reaction cavity；
(b) it heats presoma hexamethyl-methyl cyclopentadiene and closes platinum ruthenium to 50-60 DEG C, enter it with impulse form anti- Chamber is answered, starts deposition reaction when quartz glass plate reaches 150-300 DEG C in reaction chamber, is successively wrapped to an atomic layer deposition cycles It includes 20-25s hexamethyl-methyl cyclopentadiene and closes the pulse of platinum ruthenium, 10-12s exposure duration, 95-105s N2Purging, 40-45s oxygen Gas pulse, 10-12s exposure duration, 95-105s N2It purges, N in deposition process2Flow is 120-180mL/min, as needed Change the cycle-index of deposition, to obtain the Ru-Pt/TiO of different platinum ruthenium contents2Monatomic catalyst.
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