CN107335443B - The method that explosion method quickly prepares graphene-supported multimetal reforming catalyst - Google Patents
The method that explosion method quickly prepares graphene-supported multimetal reforming catalyst Download PDFInfo
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- CN107335443B CN107335443B CN201710564200.3A CN201710564200A CN107335443B CN 107335443 B CN107335443 B CN 107335443B CN 201710564200 A CN201710564200 A CN 201710564200A CN 107335443 B CN107335443 B CN 107335443B
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
Abstract
The present invention relates to the preparation field of multimetal reforming catalyst, method that specifically a kind of explosion method quickly prepares graphene-supported multimetal reforming catalyst.Graphene-supported copper cerium bimetallic catalyst is carried out in Muffle furnace, so that pressure in crucible is increased by heating, is caused the hydrone instant vaporization of graphene Inter layer adsorption and generate explosion.The present invention makes full use of the layer structure of graphene using graphene as carrier, by way of ultrasound, makes Water Molecular Adsorption in the interlayer of graphene oxide, increases with pressure as temperature is increased, hydrone vaporization, graphene layer is swelling to explode.In blast process, precursor salt is decomposed, and is generated metal oxide, is obtained that metallic particles is smaller after reduction, has prepared the graphene-supported multimetal reforming catalyst being evenly distributed.
Description
Technical field
The present invention relates to the preparation field of multimetal reforming catalyst, specifically a kind of explosion method quickly prepares graphene-supported more
The method of metallic catalyst.
Background technology
Dimethyl carbonate (DMC) is a kind of green chemical, can be used as synthetic intermediate, high-quality solvent and oil product
Additive.Carbon copper-loading catalyst is because of small toxicity, the features such as raw material is cheap and easy to get, is usually used in Synthesis of dimethyl carbonate.Graphene
Be carbon atom with sp2 hydridization be in single layer two dimensional crystal that honeycomb lattice is arranged to make up, have excellent electricity, optics, calorifics and
Mechanical performance is often used as the carrier of catalyst.Bimetallic catalyst is research hotspot in recent years, is catalyzed in traditional monometallic
On the basis of agent, second of metal is added, due to the variation of chemical composition and microstructure, bimetallic catalyst and single metal
Material, which is compared, has different property.The active site for increasing catalyst improves the reactivity and selectivity of catalyst.
The method of common bimetallic catalyst is mainly infusion process, the bimetallic catalyst Active components distribution prepared
It is uneven, it is easy to happen reunion, reduces catalytic activity, therefore wants to prepare the catalyst that particle is smaller, is evenly distributed, is opened
The preparation method of innovation is imperative.
Invention content
The present invention is uneven for the Active components distribution for solving existing bimetallic catalyst, is easy to happen reunion, reduces
The problems such as catalytic activity, provide a kind of method that explosion method quickly prepares graphene-supported multimetal reforming catalyst.
The present invention is achieved by the following technical solutions：A kind of explosion method quickly prepares graphene-supported more metal catalytics
The method of agent, includes the following steps：
(1), graphene oxide is prepared
(2), graphene-supported multimetal reforming catalyst presoma is prepared
Graphene oxide powder is mixed with the aqueous solution of at least two metal salts, 10 points are ultrasonically treated in 25 DEG C of water-baths
Clock；
Mixture after ultrasound is put into 60 DEG C of convection oven, drying and processing 12 hours obtains graphene-supported more
Metal catalyst precursor；
(3), graphene-supported multimetal reforming catalyst is prepared
Graphene-supported multimetal reforming catalyst presoma grinding, is placed in container with cover, then with the liter of 10 DEG C/min
Warm rate heats up, hear in container generation " bang " sound after, terminate heating, be cooled to room temperature；In collection vessel
Substance is subsequently placed in H2And N2It heats up and keeps the temperature in the mixed atmosphere of (carrier gas) and polymetallic oxide is restored, then
It is cooled to room temperature, graphene-supported multimetal reforming catalyst is made.
In the technical solution of the present invention " bang " sound refer to the swelling sound to explode of graphene layer, sound
Similar corn pops to form the sound of puffed rice.Why will be before graphene-supported multimetal reforming catalyst in step (3) of the present invention
Drive body grinding is placed on container with cover (non-closed), be in order to enable container in smaller pressure space is formed after heating,
Promote that graphene layer is swelling explodes.
As being further improved for technical solution of the present invention, before carrying out step (2), oxidation that step (1) prepares
Graphene powder carries out pre-treatment, and the pre-treatment step is：Load weighted graphene oxide powder is put into 25 DEG C of vacuum drying oven
In, open vacuum pump, to baking oven in vacuum degree be -0.05MPa, keep 12 hours.Carry out the graphene oxide powder phase of pre-treatment
For not carrying out the graphene oxide powder of pre-treatment, vacuum condition can remove the adsorbing contaminant in graphene oxide layer, have
Be conducive to the advantages such as Water Molecular Adsorption.
As being further improved for technical solution of the present invention, heating rate when being restored to polymetallic oxide is
3 DEG C/min, holding temperature is 450 DEG C, soaking time 2 hours.Not due to the different required holding temperatures of metal oxide
Together, but processing, simplified step, inventor test the metal oxide that metallic catalyst is often used, send out for convenience
It is now warming up to 450 DEG C and soaking time just can enough restore the various metal oxides being commonly used for 2 hours.
There is apparent advance compared with the background technology, the present invention, using graphene as carrier, make full use of graphene
Layer structure make Water Molecular Adsorption in the interlayer of graphene oxide by way of ultrasound, as temperature increases and pressure increases
Greatly, hydrone vaporizes, and graphene layer is swelling to explode.In blast process, precursor salt is decomposed, and generates metal oxide,
It obtains that metallic particles is smaller after reduction, has prepared the graphene-supported multimetal reforming catalyst being evenly distributed.This preparation method work
Skill is advanced, and data are accurately full and accurate, and preparation speed is fast, at low cost, and product is the cotton-shaped object of black, and product purity is high, reactivity
Height is twice of single-metal reforming catalyst, is the highly advanced method for quickly preparing graphene-supported multimetal reforming catalyst.
Description of the drawings
Fig. 1 is the preparation flow figure of graphene-supported multimetal reforming catalyst.Explosion is most important wherein in Muffle furnace
Process.
Fig. 2 is graphene-supported copper cerium bimetallic catalyst prepared by the embodiment of the present invention.Known in figure：Graphene is
Bright yarn shape structure, metallic particles is smaller, about 20nm, is uniformly dispersed on the surface of graphene, is not easy to form reunion.
Specific implementation mode
The chemical substance material used when specific implementation is：Graphite, potassium permanganate, sodium nitrate, copper nitrate, cerous nitrate, salt
Acid, the concentrated sulfuric acid, hydrogen peroxide, deionized water, nitrogen, hydrogen prepare dosage with gram, milliliter, centimetre3For measurement unit.
Embodiment：
(1), graphene oxide is prepared
1. configuring aqueous hydrochloric acid solution
Hydrochloric acid 10mL ± 0.001mL, deionized water 190mL ± 0.001mL are measured, is added in beaker, stirring 3min makes to mix
It closes uniformly, obtains aqueous hydrochloric acid solution.
2. preparing graphite oxide
It measures 40mL ± 0.001mL concentrated sulfuric acids to be added into 250mL beakers, for use.
2g ± 0.001g graphite powders are weighed, for use.
1.2g ± 0.001g sodium nitrate is weighed, for use.
7g ± 0.001g potassium permanganate is weighed, for use.
Beaker equipped with the concentrated sulfuric acid is placed in ice-water bath and is stirred, while it is solid that load weighted graphite powder and sodium nitrate is added
Body is slowly added to load weighted potassium permanganate solid after stirring 5min, and control temperature stirs 5min under conditions of being no more than 20 DEG C,
After be warming up to 35 DEG C of constant temperature stirring 3h, point 5 addition 250mL deionized waters are eventually adding 10mL ± 0.001mL30% dioxygens
Water continues to filter while hot after stirring 5min.
3. washing, dry graphite oxide
Filter cake is rinsed with aqueous hydrochloric acid solution twice, and after deionized water flushes three times, filter cake is put into 60 DEG C of vacuum drying
20h is dried in case.
4. preparing graphene oxide suspension
0.2g ± 0.001g graphite oxides are weighed, are put into beaker.
200mL ± 0.001mL deionized waters are measured, addition is placed in the beaker of graphite oxide, is sufficiently stirred, then ultrasonic wave
Processing 1h obtains graphene oxide suspension.
5. filtering, being dry
Graphene oxide suspension after supersound process is placed in the Buchner funnel of bottle,suction, with three layers of middling speed qualitative filter paper
It is filtered, remaining product filter cake on filter paper, filtrate liquid is evacuated in filter flask.
Filter cake is put into 60 DEG C of vacuum drying chamber and dries 12h.
(2), graphene-supported copper cerium bimetallic catalyst presoma is prepared
The preparation of graphene-supported copper cerium bimetallic catalyst presoma is ultrasonically treated in vacuum protection, air blast drying
Under conditions of complete：
1. graphene oxide pre-treatment
0.1000g ± 0.001g graphene oxide powder is weighed, 10mL beakers are put into.
Load weighted sample is put into 25 DEG C of vacuum drying oven, open vacuum pump, to baking oven in vacuum degree be-
0.05MPa is kept for 12 hours.
2. configuring copper nitrate aqueous solution
0.020g ± 0.001g copper nitrates are weighed, deionized water 2mL ± 0.001mL is measured, are added in beaker, stirring
5min, at copper nitrate aqueous solution.
3. configuring cerous nitrate aqueous solution
0.012g ± 0.001g cerous nitrates are weighed, deionized water 2mL ± 0.001mL is measured, are added in beaker, stirring
5min, at cerous nitrate aqueous solution.
4. graphene-supported copper cerium bimetallic catalyst presoma
By the graphene oxide powder after vacuum processing, the aqueous solution of copper nitrate and cerous nitrate mixes, and surpasses in 25 DEG C of water-baths
Sonication 10 minutes.
Mixture after ultrasound is put into 60 DEG C of convection oven, is dried 12 hours.
(3), graphene-supported copper cerium bimetallic catalyst is prepared
Graphene-supported copper cerium bimetallic catalyst is carried out in Muffle furnace, so that pressure in crucible is increased by heating,
Cause the hydrone instant vaporization of graphene Inter layer adsorption and generates explosion：
1. grinding
Graphene-supported copper cerium bimetallic catalyst presoma agate mortar, pestle are ground.
2. being heated in Muffle furnace
Ground graphene-supported copper cerium bimetallic catalyst presoma is weighed to be put into crucible with cover；Crucible is put
Enter in Muffle furnace, is heated up with the heating rate of 10 DEG C/min；After hearing the swelling sound of graphene layer (" bang " sound),
The temperature in Muffle furnace is 210 DEG C at this time, terminates temperature program, is cooled to room temperature.
3. restoring
The sample prepared in Muffle furnace is collected, is put into cupel.
Cupel is put into the quartz ampoule of tube furnace, in H2And N2Mixed atmosphere in restored；Heating rate be 3 DEG C/
Min rises to 450 DEG C, is kept for 2 hours, natural cooling；It is cooled to room temperature, dismantles tube furnace, take out product.
4. preserving, record
The graphene-supported multimetal reforming catalyst being prepared is fitted into sample sack, label is posted, is placed in drier,
Closed preservation.
(4), test, analysis and characterization
The color and luster of the graphene-supported multimetal reforming catalyst of preparation, Chemical Physics performance are detected, analyze, characterized.
Morphology analysis is carried out to sample with transmission electron microscope.
Conclusion：Graphene-supported multimetal reforming catalyst is loose cotton-shaped black powder, and product purity is reacted up to 99.5%
It is active high, there is good catalytic performance.
(5), activity rating
Using dimethyl carbonate in liquid phase reaction unit activity rating is carried out to catalyst is made.Activity rating condition：Cu is dense
Degree：2.6042mol/L temperature：120 DEG C, time 90min, CO：2MPa, O2：1MPa.
The active number of table 1 graphene-supported copper cerium bimetallic catalyst and graphene-supported copper catalyst of the present invention
According to comparison
Remarks：C in tableMEOH(%) refers to methanol conversion；SDMC(%) refers to the selection of dimethyl carbonate (DMC)
Property；SMF(%) refers to the selectivity of methyl formate (MF)；SDMM(%) refers to the selectivity of dimethoxym ethane (DMM)；STY(mgg-1h-1) refer to the space-time yield of dimethyl carbonate (DMC)；TOF(h-1) refer to conversion frequency.Cu/PGO described in table 1
Preparation method used by catalyst use step (2) in 3. step, other conditions, technique and raw material usage amount with
Preparation method used by Cu-Ce/PGO catalyst (step (1) to step (4)) is identical.
From in table：Compared to graphene-supported copper catalyst, the activity of the graphene-supported copper cerium of bimetallic catalyst is bright
Aobvious to improve, space-time yield is about twice of single-metal reforming catalyst.
(6), graphene-supported multimetal reforming catalyst is prepared
The preparation method of graphene-supported multimetal reforming catalyst is same as described above, and various metals salt is added in step (2)
.Other adoptable various metals salt are such as zinc nitrate, ferric nitrate and silver nitrate.Due to explosion method of the present invention
It is also applied for metal salt used in other various common metal catalyst.Above-described embodiment (graphene-supported copper cerium bimetallic
Catalyst) in graphene it is swelling when temperature be 210 DEG C, when loading other various metals salt, temperature when graphene is swelling
Between 200~220 DEG C.
Claims (2)
1. a kind of method that explosion method quickly prepares graphene-supported multimetal reforming catalyst, which is characterized in that include the following steps：
（1）, prepare graphene oxide
（2）, prepare graphene-supported multimetal reforming catalyst presoma
Step（1）The graphene oxide powder prepared carries out pre-treatment, and the pre-treatment step is：By load weighted graphite oxide
Alkene powder is put into 25 DEG C of vacuum drying oven, open vacuum pump, to baking oven in vacuum degree be 0.05MPa, keep 12 hours；It will oxidation
Graphene powder is mixed with the aqueous solution of at least two metal salts, is ultrasonically treated 10 minutes in 25 DEG C of water-baths；
Mixture after ultrasound is put into 60 DEG C of convection oven, drying and processing 12 hours obtains graphene-supported more metals
Catalyst precursor；
（3）, prepare graphene-supported multimetal reforming catalyst
Graphene-supported multimetal reforming catalyst presoma grinding, is placed in crucible with cover, then with the heating of 10 DEG C/min speed
Rate heats up, hear in crucible generation " bang " sound after, terminate heating, be cooled to room temperature；The substance in crucible is collected,
It is subsequently placed in H2And N2Mixed atmosphere in heat up and heat preservation polymetallic oxide is restored, then cool to room temperature,
Graphene-supported multimetal reforming catalyst is made.
2. the method that a kind of explosion method according to claim 1 quickly prepares graphene-supported multimetal reforming catalyst, special
Sign is that heating rate when being restored to polymetallic oxide is 3 DEG C/min, and holding temperature is 450 DEG C, soaking time
2 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4318862A (en) * | 1979-12-04 | 1982-03-09 | Anic S.P.A. | Process for producing dimethylcarbonate |
| CN105776197A (en) * | 2016-04-22 | 2016-07-20 | 泰山学院 | Surface porous graphene material and preparation method thereof |
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2017
- 2017-07-12 CN CN201710564200.3A patent/CN107335443B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4318862A (en) * | 1979-12-04 | 1982-03-09 | Anic S.P.A. | Process for producing dimethylcarbonate |
| CN105776197A (en) * | 2016-04-22 | 2016-07-20 | 泰山学院 | Surface porous graphene material and preparation method thereof |
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Inventor after: Shi Ruina Inventor after: Ren Jun Inventor after: Liu Shusen Inventor after: Zhao Jinxian Inventor after: Li Haixia Inventor after: Cheng Ming Inventor after: Hou Xiaoxiong Inventor before: Ren Jun Inventor before: Shi Ruina Inventor before: Liu Shusen Inventor before: Zhao Jinxian Inventor before: Li Haixia Inventor before: Cheng Ming Inventor before: Hou Xiaoxiong |
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