CN108816227A - Derivative carried copper-base catalyst of metal framework and preparation method thereof - Google Patents
Derivative carried copper-base catalyst of metal framework and preparation method thereof Download PDFInfo
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
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Abstract
Derivative carried copper-base catalyst of a kind of metal framework and preparation method thereof, by the way that copper source and alkali are dissolved in the water, is then mixed to get copper hydroxide suspension for copper solution and aqueous slkali；Simultaneously ultrasound is mixed after trimesic acid is dissolved with copper hydroxide suspension；Solid composite is isolated after ultrasound and is dissolved in water, silicon source is added, and the pH value of solution is adjusted with ammonium hydroxide or carbonic acid ammonium；Heating removes the ammonia in mixed liquor, and filter residue and dry solid composite are washed after filtering；Solid composite is calcined, then reduction activation in reducing atmosphere, obtains the derivative carried copper-base heterogeneous catalyst of metal framework.The preparation method simple process of the derivative carried copper-base catalyst of metal framework of the invention, reaction condition is mild, environmental-friendly, effectively reduces ethylene carbonate ester through hydrogenation and prepares methanol/ethylene glycol cost, catalytic efficiency and stability are improved, is had broad application prospects.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of derivative carried copper-base catalyst of metal framework
And preparation method thereof.
Background technique
In recent years, industry and economic fast development make problem of environmental pollution increasingly sharpen.CO2It is all carbon compounds
Final product, and it is the most cheap compound in carbon family, while being reserves carbon resource the most abundant again.Therefore,
Study CO2Effective use means have important economic value and realistic meaning.It is known as the methanol and demand of " methanol economy "
Measuring ever-increasing ethylene glycol is two kinds of important products and raw material in current chemical industry.
Based on this, by rich reserves and reproducible CO2By adding hydrogen recycling to generate methanol and ethylene glycol, to resource,
The sustainable development of energy environment and society is significant.However, CO2Thermodynamic stability and kinetic inertness limit
The development of its direct chemical utilization.Therefore, in view of CO2With ethylene oxide can industrialized production ethylene carbonate (EC), can examine
Worry catalytic hydrogenation indirect utilization CO under the conditions of relatively mild through ethylene carbonate2Methanol and ethylene glycol are produced, realizes CO2Between
Efficient utilization is connect, there is very big application potential.The pincer- of the excellent catalytic performance of excess of export is showed in the reaction system at present
Typr RuII homogeneous catalyst exists to be separated with product difficulty, and the active element noble metal Ru in its catalyst is also limited simultaneously
Its industrial applications.Therefore, the heterogeneous catalyst for developing Cheap highly effective has great significance.And heterogeneous catalyst is mainly concentrated
On a few copper-based catalysts, and its catalytic activity still needs to further increase.In recent years, carbon is with its stable physics
And chemical property and the material modified through it can limit the advantage of particle size and be concerned, some researches show that repair through carbon coating
Obvious stabilization can be obtained in the catalyst activity of decorations, and then improves catalyst stability.It therefore, can be more by metal framework derivative
Phase copper-based catalysts further promote catalyst activity and stability using the synergistic effect of carbon and copper, improve to ethylene carbonate
The catalytic efficiency of ester through hydrogenation reaction.
Currently, the copper-based catalysts for being commercially used for hydrogenation reaction mostly use infusion process, the precipitation method, ammonia still process method etc. is traditional
Carrying method preparation.Traditional carrying method process is relatively complicated and its hydrogenation catalyst performance needs to be further increased, method system
For complex process and it is not directed to carbon modification process method, preparation process is related to the high cost reagent such as soluble rare earth metal, at
This is higher, and its catalytic performance needs to be further increased.
Therefore, exploitation preparation method is easy and high catalytic efficiency, the catalyst haveing excellent performance, to meeting industrial application demand
It is significant.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of derivative carried copper-base catalysis of metal framework
Agent and preparation method thereof, at least one of to solve the above problems.
The present invention is achieved through the following technical solutions：
As one aspect of the present invention, a kind of preparation method of derivative carried copper-base catalyst of metal framework is provided,
Include the following steps：(1) copper source is dissolved in the water to obtain copper solution, alkali source is dissolved in the water to obtain aqueous slkali, then will
The copper solution and the aqueous slkali are mixed to get copper hydroxide suspension；(2) after trimesic acid being dissolved with step (1)
Obtained copper hydroxide suspension mixing, then ultrasound obtains mixed liquor；(3) mixed liquor after ultrasound is separated by solid-liquid separation, it will
It is 6~7 that obtained solid, which is washed to pH value, is then dissolved in water, silicon source is added, the pH of solution is adjusted with ammonium hydroxide or carbonic acid ammonium
Value is 10~13；(4) filter residue and dry that solid is compound is washed in the mixed liquor heating obtained step (3) except deammoniation, after filtering
Object；(5) solid composite for obtaining step (4) is calcined, and then reduction activation in reducing atmosphere obtains metal framework and spreads out
Raw carried copper-base heterogeneous catalyst.
Preferably, in step (1), copper source is one or both of copper nitrate, copper sulphate, copper chloride or copper acetate
Above combination；The alkali source is the combination of one or both of sodium hydroxide, potassium hydroxide.
Preferably, in step (2), trimesic acid is dissolved in ethyl alcohol；Ultrasonic temperature is 40~60 DEG C, and ultrasonic time is
0.5~6h.
Preferably, in step (3), the silicon source is one of silica solution, TEOS, SBA-15, MCM-41 or KIT-6.
Preferably, in step (4), filter residue deionized water, ethanol washing；Drying temperature is 50~150 DEG C, drying time
For 5~for 24 hours.
Preferably, in step (5), calcination temperature is 200~800 DEG C；Calcination time is 1~5h.
Preferably, in step (5), the reducing atmosphere is the mixed gas of hydrogen and protective gas；Wherein, described
Protective gas is the combination of one or both of nitrogen, helium or argon gas；In the mixed gas, the volume fraction of hydrogen
It is 10~100%.
Preferably, in step (5), the temperature of reduction activation is 200~600 DEG C；The reduction activation time is 1~6h.
As another aspect of the present invention, a kind of derivative load of the metal framework being prepared according to preceding method is provided
Type copper-based catalysts, the copper-based catalysts are made of copper, carbon, silicon, oxygen, the copper-based load capacity relative to monolithic catalyst
For 0.5~40wt%, the load capacity of carbon is 0.1~10%, and surplus is carrier.
Preferably, the derivative carried copper-base catalyst of the metal framework is applied to ethylene carbonate catalytic hydrogenation coproduction first
In the reacting of alcohol and ethylene glycol.
It can be seen from the above technical proposal that the derivative carried copper-base catalyst of metal framework of the invention and its preparation side
Method has the advantages that：
(1) present invention utilizes one step of ultrasonic method that Cu in conjunction with component C, is made the mutual close cooperation of Cu, C, and loaded
To carrier, the copper metal heterogeneous catalyst with higher active copper carbon nonloaded silica has been obtained, has improved catalysis effect
Rate provides new means for the preparation of copper metal catalyst.
(2) Cu metallic catalyst prepared by the present invention reacting in ethylene carbonate catalytic hydrogenation combined production of methanol and ethylene glycol
In have high catalytic efficiency and stability, for the conversion ratio of ethylene carbonate up to 100%, the selectivity of ethylene glycol is reachable
100%, the selectivity of methanol is up to 75% or more.
(3) present invention is prepared for the derivative carried copper gold of metal framework by an one-step hydrolysis precipitation method derived from metal framework
Belong to heterogeneous catalyst.The preparation process is simple, and reaction condition is mild, environmental-friendly, effectively reduces production cost, improves
Catalytic efficiency has broad application prospects.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
It is bright to be described in further detail.
The present invention provides derivative carried copper-base catalyst of a kind of metal framework and preparation method thereof, by by copper source and
Alkali is dissolved in the water, and copper solution and aqueous slkali are then mixed to get copper hydroxide suspension；By trimesic acid and dissolve
It is mixed afterwards with copper hydroxide suspension and ultrasonic；Solid composite is isolated after ultrasound and is dissolved in water, and silicon source is added,
The pH value of solution is adjusted with ammonium hydroxide or carbonic acid ammonium；Heating removes the ammonia in mixed liquor, and filter residue and dry solid are washed after filtering
Compound；Solid composite is calcined, then reduction activation in reducing atmosphere, obtains the derivative carried copper-base of metal framework
Heterogeneous catalyst.The preparation method simple process of the derivative carried copper-base catalyst of metal framework of the invention, reaction condition temperature
With, it is environmental-friendly, production cost is effectively reduced, catalytic efficiency is improved, is expected to be widely applied in industrialized production,
It has broad application prospects.
Specifically, as one aspect of the present invention, a kind of system of derivative carried copper-base catalyst of metal framework is provided
Preparation Method includes the following steps：(1) copper source is dissolved in the water to obtain copper solution, alkali source is dissolved in the water to obtain aqueous slkali,
Then the copper solution and the aqueous slkali are mixed to get copper hydroxide suspension；(2) after trimesic acid being dissolved with
The copper hydroxide suspension mixing that step (1) obtains, then ultrasound obtains mixed liquor；(3) by the mixed liquor solid-liquid after ultrasound
Separation, it is 6~7 that obtained solid, which is washed to pH value, is then dissolved in water, silicon source is added, adjusted with ammonium hydroxide or carbonic acid ammonium
The pH value of solution is 10~13；(4) filter residue and dry is washed in the mixed liquor heating obtained step (3) except deammoniation, after filtering
Solid composite；(5) solid composite for obtaining step (4) is calcined, and then reduction activation in reducing atmosphere, obtains gold
Belong to the derivative carried copper-base heterogeneous catalyst of frame.
In step (1), copper source is one or more of copper nitrate, copper sulphate, copper chloride or copper acetate
Combination；The alkali source is the combination of one or both of sodium hydroxide, potassium hydroxide.
In step (2), trimesic acid is dissolved in ethyl alcohol；Ultrasonic temperature be 40~60 DEG C, ultrasonic time be 0.5~
6h。
In step (3), the silicon source is one of silica solution, TEOS, SBA-15, MCM-41 or KIT-6.
In step (4), filter residue deionized water, ethanol washing；Drying temperature be 50~150 DEG C, drying time be 5~
24h。
In step (5), calcination temperature is 200~800 DEG C；Calcination time is 1~5h.
In step (5), the reducing atmosphere is the mixed gas of hydrogen and protective gas；Wherein, the protectiveness
Gas is the combination of one or both of nitrogen, helium or argon gas；In the mixed gas, the volume fraction of hydrogen is 10~
100%.
In step (5), the temperature of reduction activation is 200~600 DEG C；The reduction activation time is 1~6h.
As another aspect of the present invention, a kind of derivative load of the metal framework being prepared according to preceding method is provided
Type copper-based catalysts, the copper-based catalysts are made of copper, carbon, silicon, oxygen, described copper-based relative in the load of monolithic catalyst
Amount is 0.5~40wt%, and the load capacity of carbon is 0.1~10%, and surplus is carrier.
The derivative carried copper-base catalyst of the metal framework is applied to ethylene carbonate catalytic hydrogenation combined production of methanol and second
In the reaction of glycol.
Below in conjunction with specific embodiment, to derivative carried copper-base catalyst of metal framework of the invention and preparation method thereof
It is described in further detail.
Embodiment 1
An one-step hydrolysis precipitation method derived from metal framework prepare the derivative carried copper metal heterogeneous catalyst of metal framework：
(1) at room temperature, respectively by 12g Cu (NO3)2·3H2O and 4.4g NaOH is dissolved in the deionized water of equivalent, stirring
Two kinds of solution are mixed under state, obtain metal hydroxide solutions；
(2) 10g or so trimesic acid is dissolved in ethyl alcohol, mixes it with step (1) acquired solution under stirring
And the ultrasound 3h at 40 DEG C；
(3) mixed solution obtained by step (2) is subjected to washing and separates to obtain solid composite when being 6~7 to pH；
(4) step (3) obtained solid compound is dissolved in the deionized water of 400mL, ammonium hydroxide tune is used under stirring
Section pH to 10 simultaneously starts to be slowly added to 45.5083g silica solution while adjusting pH to 12, and stirs 4h；
(5) by step (4) acquired solution be heated to 80 DEG C of ammonia still processs to pH be 6~7；It is separated by filtration and uses deionized water and second
Alcohol washs to obtain solid composite.Solid composite is obtained after dry 12h at 100 DEG C；
(6) 4h will be calcined at step (5) obtained solid compound in air 400 DEG C, then in H2With N2Gaseous mixture
(H in body2Volume fraction be 10%) reduction activation 4h at 350 DEG C, obtain the derivative carried copper metal multiphase of metal framework and urge
Agent.
Performance test：
Catalyst, 20mL tetrahydrofuran and the 100 μ L that 10mmol ethylene carbonate, 5wtEC% the present embodiment are obtained
Paraxylene internal standard compound is added in stainless steel autoclave, then that autoclave is closed, successively with empty in nitrogen, hydrogen displacement kettle
After gas is multiple, 5MPa H is filled in kettle2；After checking that air-tightness is good with suds, reaction kettle is heated to 210 DEG C and is kept the temperature
4h, magnetic agitation rotating speed control are 550rpm；To after reaction, by autoclave with room temperature is dropped in ice-water bath, pass through needle-valve
Remnants H in slow release reaction kettle2, reaction kettle is opened, catalyst and reaction solution is centrifugated, takes a small amount of reaction solution with gas phase color
Its composition of spectrum analysis, EC conversion ratio are 100%, and methanol and glycol selectivity are respectively 75.0% and 99.9%.
Catalyst stability evaluation：
Catalyst that 10mmol ethylene carbonate, 5wtEC% catalyst the present embodiment are obtained, 20mL tetrahydrofuran and
100 μ L paraxylene internal standard compounds are added in stainless steel autoclave, then that autoclave is closed, are successively replaced with nitrogen, hydrogen
After air is multiple in kettle, 5MPa H is filled in kettle2；After checking that air-tightness is good with suds, reaction kettle is heated to 200 DEG C
And 4h is kept the temperature, magnetic agitation rotating speed control is 550rpm；To after reaction, by autoclave with room temperature is dropped in ice-water bath, lead to
Cross remnants H in needle-valve slow release reaction kettle2, open reaction kettle, be centrifugated catalyst and reaction solution, take a small amount of reaction solution with
Its composition of gas chromatographic analysis；When reuse by it is preceding once test separating obtained catalyst through tetrahydrofuran clean 3~5 times simultaneously
Use is separated into repetition experiment, after the 6th time is reused, up to 94.4%, methanol and ethylene glycol select EC conversion ratio
Property is respectively 76.2% and 100%.In aforementioned manners the derivative carried copper-base heterogeneous catalyst of prepared metal framework have compared with
For excellent stability.
Comparative example 1
Ammonia still process method prepares Cu SiO2Catalyst：
(1) Cu (NO of metering is weighed3)2·3H2O is dissolved in 150ml deionized water；
(2) after stirring 20min at 313K, it is slowly added into the 25-28wt% ammonium hydroxide of 30mL dropwise, controls dropwise addition process
Continue 1h, continues to stir 10min；
(3) silicon sol solution of metering is slowly dropped in above-mentioned solution, continues to stir 4h at 313K；
(4) ammonia still process will be carried out under gained mixed liquor in oil bath 363K, stopped after the pH of system is reduced to 6.5 or so
Only；
(5) gained liquid-solid mixture is filtered, while successively through deionized water and ethanol washing, then at 363K
Dry 15h；
(6) gained catalyst precursor calcines 4h, calcined catalyst in tube furnace under the conditions of nitrogen atmosphere 723K
The H for being 10% through volume fraction in 623K pipe type furnace2/N2Gaseous mixture restores 4h, obtains 25Cu@SiO2Catalyst.
Stability test
Stability test method is the same as embodiment 1, gained 25Cu@SiO2Catalyst is at 200 DEG C, 5MPa H2Lower reaction 4h first
It is secondary in use, its EC conversion ratio be 100%, MeOH and EG selectivity be respectively 59.8% and 94.3%；In the 4th repetition
82.1% is down to using rear EC conversion ratio.
Comparative example 2
(1) Cu (NO of metering is weighed3)2·3H2O, beta cyclodextrin and P123 are dissolved in 100ml deionized water and the second of 50ml
In alcohol mixed liquor；
(2) it after stirring 20min at 313K, is slowly added into the ammonium carbonate solution of the 0.5mol/L of 100mL dropwise,
Control dropwise addition process continues 1h, continues to stir 10min；
(3) ethyl orthosilicate of metering is slowly dropped in above-mentioned solution, continues to stir 4h at 313K；
(4) ammonia still process will be carried out under gained mixed liquor in oil bath 363K, stopped after the pH of system is reduced to 6.5 or so
Only；
(5) gained liquid-solid mixture is filtered, while successively through deionized water and ethanol washing, then at 363K
Dry 15h；
(6) gained catalyst precursor calcines 4h, calcined catalyst in tube furnace under the conditions of nitrogen atmosphere 723K
The H for being 10% through volume fraction in 623K pipe type furnace2/N2Gaseous mixture restores 4h, obtains 25Cu@SiO2- β-P catalyst.
Catalyst performance evaluation
Catalyst performance evaluation method is with embodiment 1, and under the same reaction conditions, the conversion ratio of EC is 64.7%, MeOH
Selectivity with EG is 58.6% and 97.4%；In contrast, copper-based heterogeneous catalyst derived from metal framework significantly improves
The selectivity of the conversion ratio of EC and MeOH and EG under the reaction system.
The comparison of 1 experimental result of table
In conclusion the preparation method simple process of the derivative carried copper-base catalyst of metal framework of the invention, reaction
Mild condition, it is environmental-friendly, production cost is effectively reduced, catalytic efficiency is improved, is expected to be widely applied to industrialize
In production, have broad application prospects.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of preparation method of the derivative carried copper-base catalyst of metal framework, which is characterized in that
Include the following steps：
(1) copper source is dissolved in the water to obtain copper solution, alkali source is dissolved in the water to obtain aqueous slkali, then by the copper solution
Copper hydroxide suspension is mixed to get with the aqueous slkali；
(2) it is mixed after dissolving trimesic acid with the copper hydroxide suspension that step (1) obtains, then ultrasound is mixed
Liquid；
(3) mixed liquor after ultrasound being separated by solid-liquid separation, it is 6~7 that obtained solid, which is washed to pH value, it is then dissolved in water,
Silicon source is added, is 10~13 with the pH value that ammonium hydroxide or carbonic acid ammonium adjusts solution；
(4) filter residue and dry solid composite are washed in the mixed liquor heating obtained step (3) except deammoniation, after filtering；
(5) solid composite for obtaining step (4) is calcined, and then reduction activation in reducing atmosphere, obtains metal framework
Derivative carried copper-base heterogeneous catalyst.
2. the preparation method of the derivative carried copper-base catalyst of metal framework according to claim 1, which is characterized in that
In step (1), copper source is the combination of one or more of copper nitrate, copper sulphate, copper chloride or copper acetate；
The alkali source is the combination of one or both of sodium hydroxide, potassium hydroxide.
3. the preparation method of the derivative carried copper-base catalyst of metal framework according to claim 1, which is characterized in that
In step (2), trimesic acid is dissolved in ethyl alcohol；Ultrasonic temperature is 40~60 DEG C, and ultrasonic time is 0.5~6h.
4. the preparation method of the derivative carried copper-base catalyst of metal framework according to claim 1, which is characterized in that
In step (3), the silicon source is one of silica solution, TEOS, SBA-15, MCM-41 or KIT-6.
5. the preparation method of the derivative carried copper-base catalyst of metal framework according to claim 1, which is characterized in that
In step (4), filter residue deionized water, ethanol washing；Drying temperature be 50~150 DEG C, drying time be 5~for 24 hours.
6. the preparation method of the derivative carried copper-base catalyst of metal framework according to claim 1, which is characterized in that
In step (5), calcination temperature is 200~800 DEG C；Calcination time is 1~5h.
7. the preparation method of the derivative carried copper-base catalyst of metal framework according to claim 1, which is characterized in that
In step (5), the reducing atmosphere is the mixed gas of hydrogen and protective gas；
Wherein, the protective gas is the combination of one or both of nitrogen, helium or argon gas；
In the mixed gas, the volume fraction of hydrogen is 10~100%.
8. the preparation method of the derivative carried copper-base catalyst of metal framework according to claim 1, which is characterized in that
In step (5), the temperature of reduction activation is 200~600 DEG C；The reduction activation time is 1~6h.
9. a kind of preparation method of the derivative carried copper-base catalyst of metal frameworks described in any item according to claim 1~8
The derivative carried copper-base catalyst of obtained metal framework, which is characterized in that
The copper-based catalysts are made of copper, carbon, silicon, oxygen, the copper-based load capacity relative to monolithic catalyst be 0.5~
40wt%, the load capacity of carbon are 0.1~10%, and surplus is carrier.
10. the derivative carried copper-base catalyst of metal framework according to claim 9, which is characterized in that the metal frame
The derivative carried copper-base catalyst of frame is applied in the reacting of ethylene carbonate catalytic hydrogenation combined production of methanol and ethylene glycol.
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| CN110227545A (en) * | 2019-06-28 | 2019-09-13 | 华东师范大学 | It is a kind of for the catalyst of ethylene carbonate hydrogenation reaction and its preparation and application |
| CN116463034A (en) * | 2023-05-21 | 2023-07-21 | 广州润泰新材料科技有限公司 | High-temperature-resistant fireproof coating material and preparation method and application thereof |
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