CN109926066A - Double auxiliary agent nano Pd catalyst Preparation method and uses - Google Patents
Double auxiliary agent nano Pd catalyst Preparation method and uses Download PDFInfo
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- CN109926066A CN109926066A CN201910256655.8A CN201910256655A CN109926066A CN 109926066 A CN109926066 A CN 109926066A CN 201910256655 A CN201910256655 A CN 201910256655A CN 109926066 A CN109926066 A CN 109926066A
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Abstract
The present invention relates to double auxiliary agent nano Pd catalyst Preparation method and uses, the resulting double auxiliary agent nano Pd catalysts of preparation method of the present invention: including carrier, active component and auxiliary agent；The carrier is Al2O3；The active component is palladium；The auxiliary agent is copper and mickel；Wherein, on the basis of the carrier quality, the load capacity of the active component is 0.05%-1.5%.Carrying method in situ used in the present invention can be carried out at normal temperature, and reaction condition is mild, and easy to operate, low energy consumption, substantially save economic cost, and method for preparing catalyst of the invention is more suitable industrialized production.
Description
Technical field
The present invention relates to ethylene glycol production technical fields, and in particular to double auxiliary agent nano Pd catalyst preparation methods and use
On the way.
Background technique
Ethylene glycol is a kind of important organic solvent and Organic Chemicals, widely used, wherein 90% or more is used for
Polyester dacron is prepared, remaining be used to produce antifreezing agent, adhesive, paint solvent and condensing agent etc..Currently, China's ethylene glycol year
Yield is far below demand, needs from a large amount of imports in the area such as Northeast Asia, the Middle East and North America, and import dependency degree is very high, because
This, the sustainable development that research and development ethylene glycol production technology is related to ethylene glycol industry to the country is of great significance.
The production of the ethylene glycol of China's industry at present mainly uses conventional petroleum base route, and production process passes through petroleum fissure first
Solution production ethylene, reoxidizes generation ethylene oxide, ethylene glycol is made in last ethylene oxide direct hydration.Although this petroleum base road
Line technology relative maturity, but there are energy consumption height, production procedure length, product separation and purification unit process water consumption are big and selective
Problem relatively low, by-product is more.
China's fossil energy design feature are as follows: more coals, oil starvation, few gas, therefore develop coal based synthetic gas and prepare ethylene glycol not
Only adapt to the fossil energy design feature in China, and the imbalance between supply and demand that will largely alleviate China's ethylene glycol market.
It is main that coal based synthetic gas prepares ethylene glycol comprising the following three steps: (1) carbon monoxide dehydrogenation purifies；(2) carbon monoxide and Asia
Methyl nitrate is coupled dimethyl oxalate processed；(3) preparation of ethanediol by dimethyl oxalate hydrogenation.Wherein, carbon monoxide and nitrous acid first
It is that coal based synthetic gas prepares one of key link of ethylene glycol that ester coupling, which prepares dimethyl oxalate,.Carbon monoxide and methyl nitrite
The main chemical reactions formula for being coupled dimethyl oxalate process processed is as follows:
2CH3ONO+2CO→(COOCH3)2+2NO (1)
2CH3OH+2NO+0.5O2→2CH3ONO+H2O (2)
The NO that carbon monoxide and methyl nitrite synthesizing dimethyl oxalate process (step (1)) generate, in step (2) with
Methanol and oxygen reaction generate new methyl nitrite, so that raw material methyl nitrite is recycled, thus, the process
The target for realizing " feedstock circulation utilization, green production ", meets the ecological requirements of current industrialized production.Coupling process is always anti-
Shown in Ying Shiru formula (3).The coupling process is with easy to operate, reaction condition is mild, low in raw material price, atom utilization are high
And the characteristics of safety non-pollution.
2CO+2CH3OH+0.5O2→(COOCH3)2+H2O (3)
CO coupling prepares dimethyl oxalate process frequently with precious metals pd as catalyst activity component, it is seen that patent report
Pd load capacity is generally higher (1% or so) in road, and Pd is a kind of noble metal, and resource is limited on earth, the Pd of high load amount
Catalyst cost is caused to increase, thus, on the basis of guaranteeing catalytic efficiency, the dosage for reducing Pd in catalyst has important valence
Value.
Chinese patent CN107175104A report, utilize ultrasonic disperse technology and microwave heating preconditioning technique to handle Pd
The method of precursor solution, it is possible to reduce loss of the precious metals pd in catalyst preparation process improves the actual negative carrying capacity of Pd,
Prepared catalyst is applied to be prepared in the reacting of dimethyl oxalate in CO and methyl nitrite coupling, and dimethyl oxalate space-time is received
Rate is 600mlL-1·h-1.Chinese patent CN106378128A is by Pd and α-Al2O3It impregnates, and rises under nitrogen protection simultaneously
Temperature obtains Pd load capacity 0.5% (catalyst carrier quality meter), Pd base of good performance to 500-800 DEG C of constant temperature processing
Catalyst.
There is research to confirm can use synergistic effect and nanoparticle small-size effect between metal to improve catalyst
Activity and selectivity.Chinese patent CN105396584A uses the bridged adsorption that lanthanide series metal or its oxide is added to regulate and control Pd
And wire type absorption ratio between 0.8~4.5, to improving the selectivity of catalyst to 96%.Chinese patent
CN106925263A, using polyvinyl alcohol or polypropylene amine water-soluble polymer as surfactant, has using strontium or barium as auxiliary agent
Effect control nano-particles size is in 10nm hereinafter, and having active metal in the dispersion degree of carrier surface to be obviously improved.
In view of the economy of auxiliary agent, Chinese patent CN1034041826 is reported to be prepared using room temperature original position load method
Pd-Cu/α-Al2O3Duplex metal nano granule, average-size is 3~4nm, in terms of catalyst carrier quality, successfully by active group
Divide the load capacity of Pd to be reduced to 0.1%, and maintain the high activity and high stability of catalyst, realizes noble metal catalyst
Part substitution, saved catalyst cost.
Summary of the invention
It is described in order to solve the above technical problem, the present invention provides a kind of preparation method of double auxiliary agent nano Pd catalysts
Double auxiliary agent nano Pd catalysts include: carrier, active component and auxiliary agent；The carrier is Al2O3；The active component is palladium；Institute
Stating auxiliary agent is copper and mickel；Wherein, on the basis of the carrier quality, the load capacity of the active component is 0.05%-1.5%；
Include the following steps:
Step 1): a certain amount of palladium source, copper source, nickel source, surfactant, organic complexing agent and deionization are accurately weighed
Water is configured to mixed solution；
Step 2): the carrier is added in the mixed solution, the ultrasound 5-30min at ultrasonic power 80-100W,
Then the uniform stirring 0.5-2h at 25-35 DEG C, obtains suspension；
Reducing agent: being configured to the reducing agent solution of 0.1-0.5mol/L by step 3), and the reducing agent solution is added to
In the suspension, after 4-12h is stirred at room temperature, continuation is aged 6-60h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, obtained solid product in vacuum exsiccator,
At -0.1MPa, 35-55 DEG C, dry 24-36h.
Further, the molar ratio of the palladium and the copper, the nickel is Pd:Cu:Ni=(1-2): (1.5-4): (0.5-
1.5)。
Further, the carrier is α-Al2O3、β-Al2O3And/or γ-Al2O3In any one or it is any two kinds with
On combination.
Further, the specific surface area of the carrier is 1-30m2/ g, average pore size 1-20nm, specific pore volume 0.001-
0.02cm3/g。
Further, any one of the palladium source in sodium tetrachloropallate, tetrachloro-palladium potassium chlorate and/or tetrachloro-palladium acid ammonium
Or any two or more combination.
Further, copper source in copper chloride, copper nitrate and/or copper sulphate any one or it is any two kinds with
On combination.
Further, the nickel source in nickel chloride, nickel nitrate and/or nickel sulfate any one or it is any two kinds with
On combination.
Further, the surfactant is selected from polyvinylpyrrolidone, cetyl trimethylammonium bromide, dodecane
Any one or any two or more combinations in base benzene sulfonic acid sodium salt and/or lauryl sodium sulfate.
Further, the organic complexing agent is in anhydrous citric acid, ethylenediamine tetra-acetic acid and/or calgon
Any one or any two or more combinations.
Further, the temperature in the step 2) is 30 DEG C.
The present invention also provides a kind of purposes of double auxiliary agent nano Pd catalysts, it is used for preparing dimethyl oxalate anti-
The catalyst answered.
Beneficial effects of the present invention
1, double auxiliary agent nano Pd catalysts of the invention using Cu and Ni as auxiliary agent so that receiving of being prepared of the present invention
Rice palladium catalyst grain diameter size in 3~5nm, be evenly distributed, be more conducive to improve reaction efficiency；
2, double auxiliary agent nano Pd catalysts of the invention, by introducing Cu and Ni bimetallic, in conjunction with active component Pd, benefit
With the synergistic effect and nano particle small-size effect between various metals, the part substitution of precious metals pd, drop are not only realized
The low production cost of catalyst, also further improves the performance of catalyst on the basis of existing catalyst；
3, double auxiliary agent nano Pd catalysts of the invention have well under Pd low-load amount (preferably load capacity is 0.5%)
Catalytic activity MN conversion per pass is 85~96%, dimethyl oxalate selectively up to 97%；
4, the carrying method in situ used in the present invention can be carried out at normal temperature, and reaction condition is mild, easy to operate, energy
It consumes low, greatly saves economic cost, and method for preparing catalyst of the invention is more suitable industrialized production.
Detailed description of the invention
Fig. 1-a is that the TEM of 2 gained sample of embodiment schemes；
Fig. 1-b is that the TEM of 3 gained sample of embodiment schemes；
Fig. 2-a is that the TME of 8 gained sample of embodiment schemes；
Fig. 2-b is that the TEM of 9 gained sample of embodiment schemes；
Fig. 3 is that the TEM of 10 gained sample of embodiment schemes.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiments of the present invention, instead of all the embodiments.
Embodiment 1
Step 1): 0.0423g sodium tetrachloropallate, 0.018g copper chloride, 0.0167g nickel chloride, 0.666g polyethylene are weighed
Pyrrolidones, 0.63g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): it takes reducing agent ascorbic acid 0.28g to be added to and is configured to going back for 0.318mol/L in the deionized water of 5ml
The reducing agent solution is added in the suspension by former agent solution, and after 8h is stirred at room temperature, continuation is aged at room temperature
8h；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 1.
It uses sample 1 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation
Experiment, step include: by 1 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, the catalyst granules loading for weighing 0.5g is consolidated
It is filled with quartz sand at the both ends of the flat-temperature zone of fixed bed reactor, the fixed bed reactors；CO in unstripped gas: methyl nitrite
Volume ratio is 1.25:1, air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C, and products therefrom is online by gas-chromatography
Monitoring is analyzed, and analysis the results are shown in Table 1.
Embodiment 2
Step 1): 0.0423g sodium tetrachloropallate, 0.036g copper chloride, 0.0167g nickel chloride, 0.666g polyethylene are weighed
Pyrrolidones, 0.63g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged 8h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 2.
It uses sample 2 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation
Experiment, comprising: by 2 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixed bed of 0.5g
It is filled with quartz sand at the both ends of the flat-temperature zone of reactor, the fixed bed reactors；CO in unstripped gas: the volume of methyl nitrite
Than for 1.25:1, air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C.Products therefrom is monitored on-line by gas-chromatography
It is analyzed, analysis the results are shown in Table 1.
Embodiment 3
Step 1): 0.0423g sodium tetrachloropallate, 0.048g copper chloride, 0.0167g nickel chloride, 0.666g polyethylene are weighed
Pyrrolidones, 0.63g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged 8h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 3.
It uses sample 3 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation
Experiment, comprising: by 3 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixed bed of 0.5g
It is filled with quartz sand at the both ends of the flat-temperature zone of reactor, the fixed bed reactors；CO in unstripped gas: the volume of methyl nitrite
Than for 1.25:1, air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C.Products therefrom is monitored on-line by gas-chromatography
It is analyzed, analysis the results are shown in Table 1.
Embodiment 4
Step 1): 0.0423g sodium tetrachloropallate, 0.036g copper chloride, 0.0835g nickel chloride, 0.666g polyethylene are weighed
Pyrrolidones, 0.63g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged 8h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 4.
It uses sample 4 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation
Experiment, comprising: by 4 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixed bed of 0.5g
It is filled with quartz sand at the both ends of the flat-temperature zone of reactor, the fixed bed reactors；CO in unstripped gas: the volume of methyl nitrite
Than for 1.25:1, air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C, and products therefrom is monitored on-line by gas-chromatography
It is analyzed, analysis the results are shown in Table 1.
Embodiment 5
Step 1): 0.0423g sodium tetrachloropallate, 0.036g copper chloride, 0.02505g nickel chloride, 0.666g polyethylene are weighed
Pyrrolidones, 0.63 anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged 8h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 5.
It uses sample 5 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation
Experiment, comprising: by 5 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixed bed of 0.5g
It is filled with quartz sand at the both ends of the flat-temperature zone of reactor, the fixed bed reactors；CO in unstripped gas: the volume of methyl nitrite
Than for 1.25:1, air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C.Products therefrom is monitored on-line by gas-chromatography
It is analyzed, analysis the results are shown in Table 1.
Embodiment 6
Step 1): 0.0423g sodium tetrachloropallate, 0.018g copper chloride, 0.0167g nickel chloride, 0.333g polyethylene are weighed
Pyrrolidones, 0.63g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged 8h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 6.
It uses sample 6 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation,
Include: by 6 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixed bed reaction of 0.5g
It is filled with quartz sand at the both ends of the flat-temperature zone of device, the fixed bed reactors；CO in unstripped gas: the volume ratio of methyl nitrite is
1.25:1, gas phase air speed are 4000mlh-1·g-1, reaction temperature is 125 DEG C.Products therefrom is monitored on-line by gas-chromatography
It is analyzed, analysis the results are shown in Table 1.
Embodiment 7
Step 1): 0.0423g sodium tetrachloropallate, 0.018g copper chloride, 0.0167g nickel chloride, 1.332g polyethylene are weighed
Pyrrolidones, 0.63g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged 8h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 7.
It uses sample 7 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation
Experiment, comprising: by 7 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixed bed of 0.5g
It is filled with quartz sand at the both ends of the flat-temperature zone of reactor, the fixed bed reactors；CO in unstripped gas: the volume of methyl nitrite
Than for 1.25:1, air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C.Products therefrom is monitored on-line by gas-chromatography
It is analyzed, analysis the results are shown in Table 1.
Embodiment 8
Step 1): 0.0423g sodium tetrachloropallate, 0.018g copper chloride, 0.0167g nickel chloride, 0.666g polyethylene are weighed
Pyrrolidones, 0.315g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged 8h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 8.
It uses sample 8 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation,
Include: by 8 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixed bed reaction of 0.5g
It is filled with quartz sand at the both ends of the flat-temperature zone of device, the fixed bed reactors；CO in unstripped gas: the volume ratio of methyl nitrite is
1.25:1 air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C.Products therefrom is monitored on-line by gas-chromatography and is carried out
Analysis, analysis the results are shown in Table 1.
Embodiment 9
Step 1): 0.0423g sodium tetrachloropallate, 0.018g copper chloride, 0.0167g nickel chloride, 0.666g polyethylene are weighed
Pyrrolidones, 0.945g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged 8h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 9.
It uses sample 9 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation
Experiment, comprising: by 9 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixed bed of 0.5g
It is filled with quartz sand at the both ends of the flat-temperature zone of reactor, the fixed bed reactors；CO in unstripped gas: the volume of methyl nitrite
Than for 1.25:1, air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C.Products therefrom is monitored on-line by gas-chromatography
It is analyzed, analysis the results are shown in Table 1.
Embodiment 10
Step 1): 0.0423g sodium tetrachloropallate, 0.036g copper chloride, 0.0167g nickel chloride, 0.666g polyethylene are weighed
Pyrrolidones, 0.63g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged 16h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 10.
It uses sample 10 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation
Experiment, comprising: by 10 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixation of 0.5g
The flat-temperature zone of bed reactor, the both ends of the fixed bed reactors are filled with quartz sand；CO in unstripped gas: the body of methyl nitrite
Product is than being 1.25:1, air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C.Products therefrom is supervised online by gas-chromatography
Survey is analyzed, and analysis the results are shown in Table 1.
Embodiment 11
Step 1): 0.0423g sodium tetrachloropallate, 0.036g copper chloride, 0.0167g nickel chloride, 0.666g polyethylene are weighed
Pyrrolidones, 0.315g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged for 24 hours at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 11.
Use sample 11 as catalyst, progress CO prepares dimethyl oxalate catalyst performance with methyl nitrite coupling and comments
Valence, comprising: by 11 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixed bed of 0.5g
It is filled with quartz sand at the both ends of the flat-temperature zone of reactor, the fixed bed reactors；CO in unstripped gas: the volume of methyl nitrite
Than for 1.25:1, air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C.Products therefrom is monitored on-line by gas-chromatography
It is analyzed, analysis the results are shown in Table 1.
Embodiment 12
Step 1): 0.0423g sodium tetrachloropallate, 0.036g copper chloride, 0.0167g nickel chloride, 0.666g polyethylene are weighed
Pyrrolidones, 0.63g anhydrous citric acid and 45ml deionized water, are configured to mixed solution；
Step 2): 3g α-Al is taken2O3Carrier is added in the mixed solution, the ultrasound 10min at ultrasonic power 100W,
Then the uniform stirring 0.5h at 30 DEG C, obtains suspension；
Step 3): take reducing agent ascorbic acid 0.28g be added to be configured in the water of 5ml 0.318mol/L reducing agent it is molten
The reducing agent solution is added in the suspension by liquid, and after 8h is stirred at room temperature, continuation is aged 48h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, will after obtained solid product is washed with water 6 times
The solid product is dried in vacuum exsiccator, and vacuum drying oven is set as -0.1MPa, 50 DEG C, and 32h is dried, obtains
To sample 12.
It uses sample 12 as catalyst, carries out CO and methyl nitrite coupling prepares dimethyl oxalate catalyst performance evaluation
Experiment, comprising: by 12 tabletting of sample, it is broken, sieve as the particle of 40-60 mesh, weigh the catalyst granules loading fixation of 0.5g
The flat-temperature zone of bed reactor, the both ends of the fixed bed reactors are filled with quartz sand；CO in unstripped gas: the body of methyl nitrite
Product is than being 1.25:1, air speed 4000mlh-1·g-1, reaction temperature is 125 DEG C.Products therefrom is supervised online by gas-chromatography
Survey is analyzed, and analysis the results are shown in Table 1.
1 reaction result of table
Fig. 1-a is the TEM figure that embodiment 2 prepares gained sample, and Fig. 1-b is the TEM figure that embodiment 3 prepares gained sample,
As it can be seen that with the increase of Cu dosage, nano particle average grain diameter increases to 6.5nm from 4nm, in conjunction with catalyst performance in table 1
Data analysis it is found that Cu:Pd molar ratio in 0.75-1.5 range, with the increase of Cu dosage, catalyst activity and
Selectivity increases therewith, after the molar ratio of Cu:Pd is more than 1.5, excessive CuCl2It is covered on the active site of active component
On, lead to particle agglomeration, nano-particles size becomes larger, and catalytic efficiency reduces.
Fig. 2-a is that the TEM of 8 gained sample of embodiment schemes, and Fig. 2-b is that the TEM of 9 gained sample of embodiment schemes, can from figure
Know, as anhydrous citric acid (C6H8O7): when the molar ratio of Pd increases to 24 by 12, nano particle average grain diameter is reduced by 17.04nm
To 9.34nm, while dispersion degree also makes moderate progress；As anhydrous citric acid (C6H8O7): when the molar ratio of Pd is 12, partial particulate group
It is poly-, it is seen then that the increase of anhydrous citric acid dosage has facilitation for preparing little particle nanoparticle in reduction process.
Fig. 3 is that the TEM of 10 gained sample of embodiment schemes, and nano particle average grain diameter is 3.57nm, prepares institute with embodiment 2
The catalyst granules minimum dimension of the sample obtained is compared for 4.0nm, illustrates that extending digestion time can reduce the grain of nano particle
Diameter size, the dispersibility for improving nano particle.
Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without making creative work
The every other embodiment obtained, shall fall within the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of double auxiliary agent nano Pd catalysts, which is characterized in that double auxiliary agent nano Pd catalysts include:
Carrier, active component and auxiliary agent；The carrier is Al2O3；The active component is palladium；The auxiliary agent is copper and mickel；Wherein, with
On the basis of the carrier quality, the load capacity of the active component is 0.05%-1.5%；
Include the following steps:
Step 1): a certain amount of palladium source, copper source, nickel source, surfactant, organic complexing agent and deionized water are accurately weighed, is matched
Mixed solution is made；
Step 2): the carrier is added in the mixed solution, the ultrasound 5-30min at ultrasonic power 80-100W, then
Uniform stirring 0.5-2h, obtains suspension at 25-35 DEG C；
Reducing agent: being configured to the reducing agent solution of 0.1-0.5mol/L by step 3), the reducing agent solution is added to described
In suspension, after 4-12h is stirred at room temperature, continuation is aged 6-60h at room temperature；
Step 4): the product that the step 3) obtains is separated by filtration, obtained solid product in vacuum exsiccator, in-
At 0.1MPa, 35-55 DEG C, dry 24-36h.
2. preparation method according to claim 1, which is characterized in that the molar ratio of the palladium and the copper, the nickel is
Pd:Cu:Ni=(1-2): (1.5-4): (0.5-1.5).
3. preparation method according to claim 1, which is characterized in that the carrier is α-Al2O3、β-Al2O3And/or γ-
Al2O3In any one or any two or more combinations.
4. preparation method according to claim 1, which is characterized in that the specific surface area of the carrier is 1-30m2/ g, it is average
Aperture is 1-20nm, specific pore volume 0.001-0.02cm3/g。
5. preparation method according to claim 1-4, which is characterized in that the palladium source be selected from sodium tetrachloropallate,
Any one or any two or more combinations in tetrachloro-palladium potassium chlorate and/or tetrachloro-palladium acid ammonium.
6. preparation method according to claim 5, which is characterized in that copper source is selected from copper chloride, copper nitrate and/or sulphur
Any one or any two or more combinations in sour copper.
7. preparation method according to claim 5, which is characterized in that the nickel source is selected from nickel chloride, nickel nitrate and/or sulphur
Any one or any two or more combinations in sour nickel.
8. preparation method according to claim 5, which is characterized in that the surfactant is selected from polyvinylpyrrolidine
In ketone, cetyl trimethylammonium bromide, neopelex and/or lauryl sodium sulfate any one or it is any
Two or more combinations.
9. the purposes of double auxiliary agent nano Pd catalysts, feature obtained by a kind of any one of claim 1-8 preparation method exist
In as the catalyst for preparing dimethyl oxalate reaction.
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| CN114433081A (en) * | 2022-02-25 | 2022-05-06 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for CO-production of carbonic ester and formic ester by synthesizing oxalate with CO |
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