CN104399498A - Carbon nanotube-graphene catalyst for synthesizing diethyl carbonate, and preparation method thereof - Google Patents
Carbon nanotube-graphene catalyst for synthesizing diethyl carbonate, and preparation method thereof Download PDFInfo
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- CN104399498A CN104399498A CN201410555090.0A CN201410555090A CN104399498A CN 104399498 A CN104399498 A CN 104399498A CN 201410555090 A CN201410555090 A CN 201410555090A CN 104399498 A CN104399498 A CN 104399498A
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Abstract
The present invention discloses a carbon nanotube-graphene loaded copper palladium catalyst PdCl2/Cu-nanotube-graphene for synthesizing diethyl carbonate through gas-phase carbonyl oxidation, wherein the carrier of the catalyst is a carbon nanotube-graphene composite material, the active component is any one selected from a divalent copper salt such as CuCl2, Cu(NO3)2, Cu(CH3COO)2 and CuSO4, the auxiliary agent of the catalyst is PdCl2, the copper doping amount is 0.1-2% of the carrier mass, and the palladium loading amount is 0.010-0.025% of the carrier mass. According to the invention, the prepared catalyst is used for the diethyl carbonate synthesis reaction through the gas-phase ethanol oxidation, the conversion rate of the target product diethyl carbonate is high, and the selectivity is good.
Description
Technical field
The present invention relates to a kind of CNT-graphen catalyst for the synthesis of diethyl carbonate and preparation method thereof, belong to the gas phase catalytic synthesis technology of diethyl carbonate.
Background technology
Diethyl carbonate (Diethyl Carbonate; vehicle economy C) be important substance in carbonic ester; there is purposes widely; owing to containing ethyl, ethyoxyl, carbonyl and carbonyl ethyoxyl in its molecular structure; thus chemical property is very active; can react with compounds such as alcohol, phenol, amine, esters, be important organic synthesis intermediate, there is very high industrial application value.When DEC is discharged in environment, carbon dioxide and the harmless product of ethanol two kinds can be decomposed into lentamente, be belonged to good green chemical.DEC can be used as solvent, in the fixing paint of vacuum tube cathode, as surfactant and lithium battery solution additive etc.Diethyl carbonate containing oxygen value (40.6%) far above methyl tertiary butyl ether(MTBE) (MTBE) (18.2%), can as the oxygenated additive of gasoline, improve the combustibility of gasoline, the discharge of decreasing pollution thing.The use of MTBE is progressively limited in the U.S., in possible substitute, the oil/water distribution coefficient of DEC and anti-volatility are better than dimethyl carbonate (DMC) and ethanol, therefore, DEC, using one of substitute as MTBE, has more competitive advantage than DMC and ethanol.The main method of current synthesis DEC has phosgenation, ester-interchange method, liquid phase method, oxidation oxo synthesis and carbon monoxide growth by lower pressure phase method etc.
Ethanol gas phase oxidation carbonylation synthesis DEC is one of promising process route of most.The ethanol coming from living beings can be adopted to be reactant, under Cu-series catalyst effect, gaseous oxidation carbonylation synthesis DEC.The accessory substance of reaction is harmless water, and Atom economy is good, meets the requirement of Green Chemistry, is current green chemistry process of generally acknowledging in the world, becomes the focus competitively developed both at home and abroad, have tempting industrial prospect.In addition, rich coal resources in China, raw material is easy to get, CO wide material sources, and therefore the development of the Coal Chemical Industry be expected to China, carbon one chemical industry is also played huge impetus by the research of diethyl carbonate.The reaction equation of this technique is as follows:
Adopt the research of vapor phase method oxidation carbonylation synthesis DEC at the early-stage at present in the world, mainly activated carbon supported chloride catalyst and Solid-state Ion-exchange molecular sieve catalyst.Activated carbon supported chloride catalyst, the chlorine of existence runs off, poor catalyst stability and equipment corrosion problem, and Solid-state Ion-exchange type catalyst activity is lower, selective undesirable.To sum up, urgently develop a kind of good stability, the catalyst that selection type is high.
Summary of the invention
The object of the present invention is to provide a kind of CNT-graphen catalyst for the synthesis of diethyl carbonate and preparation method thereof.Catalyst obtained in this way has active good, selective height, the feature that conversion ratio is high.
The present invention is realized by following technical proposals, a kind of catalyst for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation, described carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation technique, is be CO: O in feedstock mol ratio
2=2: 1 ~ 22: 1, reaction temperature is 100 ~ 180 DEG C, and reaction pressure is realize under 0.2 ~ 1.0MPa and catalyst existent condition, and it is characterized in that, the catalyst adopted is PdCl
2/ Cu-CNT-Graphene; The carrier of catalyst is carbon nanometer tube-graphene composite material, and active component is cupric salt (CuCl
2, Cu (NO
3)
2or Cu (CH
3cOO)
2), the auxiliary agent of catalyst is PdCl
2, Copper-cladding Aluminum Bar amount is 0.1% ~ 2% of carrier quality, and palladium load capacity is 0.010% ~ 0.025% of carrier quality; As gas space velocity 2500 ~ 5000h
-1time, the consumption of catalyst is 0.5 ~ 2g.
In above-mentioned catalyst, carrier is carbon nanometer tube-graphene composite material.
Above-mentioned catalyst activity component is cupric salt (CuCl
2, Cu (NO
3)
2, Cu (CH
3cOO)
2or CuSO
4).
The preparation method of above-mentioned catalyst, is characterized in that comprising following process: graphite oxide roasting 1h at 900 DEG C in Muffle furnace of first will dry, obtained expanded graphite; Copper doped on expanded graphite subsequently, is immersed in the aqueous solution of ammonium carbonate by expanded graphite, dropwise instills in above-mentioned solution under agitation by the aqueous solution containing cupric salt, stirs, leaves standstill, filters, dries, grind to form fine powder after roasting 1h; Finally above-mentioned fine powder is put in chemical vapor deposition stove, pass into carbon-source gas, obtain the CNT of copper doped and the compound of Graphene by chemical vapour deposition (CVD), then carry out dip loading auxiliary agent PdCl
2, drying obtains copper palladium CNT-graphen catalyst.
The invention has the advantages that, obtaining CNT-graphen catalyst, with other simple loaded catalysts as CuCl by adopting vapour deposition process
2-PdCl
2/ AC (active carbon) compares, and catalyst activity is stablized, and the service life of catalyst reaches more than 80h, is 5 times of existing catalyst service life.
Below by specific embodiment, the present invention is further illustrated, but do not limited the present invention.
Detailed description of the invention
[embodiment 1]
First, by 2g graphite oxide roasting 1h at 900 DEG C in Muffle furnace of drying, obtained expanded graphite; Copper doped on expanded graphite subsequently, is immersed in the aqueous solution 40ml of 1mol/L ammonium carbonate by expanded graphite, under agitation will containing CuCl
2the aqueous solution 10ml of 0.5g dropwise instills in above-mentioned solution, stirs, leaves standstill, filters, dries, grind to form fine powder 2.3g after roasting 1h; Finally above-mentioned fine powder is put in chemical vapor deposition stove, pass into carbon-source gas methane, obtain the CNT of copper doped and the compound of Graphene by chemical vapour deposition (CVD), then the CNT of 3g cupric and Graphene are joined the PdCl of 50mL
2flood 4h in methanol solution, revolve steaming, shaping obtained copper palladium CNT-graphen catalyst 3g.
[embodiment 2]
Under the preparation condition and the identical situation of embodiment 1 of catalyst, only change the copper source in preparation method into Cu (NO
3)
2mantoquita, obtains catalyst 3g.
[embodiment 3]
Under the preparation condition and the identical situation of embodiment 1 of catalyst, only change the copper source in preparation method into Cu (CH
3cOO)
2h
2o mantoquita, obtains catalyst 3g.
[embodiment 4]
Under the preparation condition and the identical situation of embodiment 1 of catalyst, only change the copper source in preparation method into CuSO
4mantoquita, obtains catalyst 3g.
[embodiment 5]
Under the preparation condition and the identical situation of embodiment 1 of catalyst, only change the carbon-source gas in preparation method into ethene, obtain catalyst 3g.
[embodiment 6]
Under the preparation condition and the identical situation of embodiment 1 of catalyst, only change the carbon-source gas in preparation method into ethane, obtain catalyst 3g.
[reaction embodiment 7-12]
In pressurization minisize reaction system, carry out the activity rating of catalyst, pass into reactant CO (80mL/min), O
2(1080mL/min) and carrier gas N
2(50mL/min), ethanol adds reactor by pressurization trace quantity pump with constant flow rate 0.1mL/min, and each 1.5g of catalyst obtained by the embodiment 1 ~ 6 using catalyst preparing respectively, at 140 DEG C, 0.7MPa reacts.With ethanol conversion, ethanol to the selective of DEC and diethyl carbonate space-time yield for index, gained reactivity worth is as shown in table 1.
The reaction result of table 1 catalytic oxidation carbonylation synthesis diethyl carbonate
[reaction embodiment 13-16]
In pressurization minisize reaction system, carry out the activity rating of catalyst, pass into reactant CO (80mL/min), O
2(1080mL/min) and carrier gas N
2(50mL/min), ethanol adds reactor by pressurization trace quantity pump with constant flow rate 0.1mL/min, and each 1.5g of catalyst obtained by the embodiment 1,3,4,6 using catalyst preparing respectively, at 120 DEG C, 0.6MPa reacts.With ethanol conversion, ethanol to the selective of DEC and diethyl carbonate space-time yield for index, gained reactivity worth is as shown in table 2.
Table 2 is oxidized the catalytic activity of carbonylation synthesis diethyl carbonate catalyst
Claims (2)
1. the CNT for gaseous oxidation carbonylation synthesis diethyl carbonate-graphene-supported copper palladium catalyst PdCl
2/ Cu-CNT-Graphene, is characterized in that, the carrier of catalyst is carbon nanometer tube-graphene composite material, and active component is cupric salt CuCl
2, Cu (NO
3)
2, Cu (CH
3cOO)
2or CuSO
4any one, the auxiliary agent of catalyst is PdCl
2, Copper-cladding Aluminum Bar amount is 0.1% ~ 2% of carrier quality, and palladium load capacity is 0.010% ~ 0.025% of carrier quality.
2. the CNT for gaseous oxidation carbonylation synthesis diethyl carbonate according to claim 1-graphene-supported copper palladium catalyst PdCl
2the preparation method of/Cu-CNT-graphen catalyst, it is characterized in that comprising following process: graphite oxide roasting 1h at 900 DEG C in Muffle furnace of first will dry, obtained expanded graphite, copper doped on expanded graphite subsequently, be immersed in the aqueous solution of ammonium carbonate by expanded graphite, under agitation will containing cupric salt CuCl
2, Cu (NO
3)
2, Cu (CH
3cOO)
2or CuSO
4the aqueous solution of any one dropwise add in above-mentioned solution, through stirring, leaving standstill, filter, dry, fine powder is ground to form after roasting 1h, finally above-mentioned fine powder is put in chemical vapor deposition stove, pass into carbon-source gas, obtain the CNT of copper doped and the compound of Graphene by chemical vapour deposition (CVD), then carry out dip loading auxiliary agent PdCl
2, drying obtains PdCl
2/ Cu-CNT-graphen catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410555090.0A CN104399498A (en) | 2014-10-15 | 2014-10-15 | Carbon nanotube-graphene catalyst for synthesizing diethyl carbonate, and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410555090.0A CN104399498A (en) | 2014-10-15 | 2014-10-15 | Carbon nanotube-graphene catalyst for synthesizing diethyl carbonate, and preparation method thereof |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107262095A (en) * | 2017-07-20 | 2017-10-20 | 太原理工大学 | The preparation method of Copper-cladding Aluminum Bar graphen catalyst |
| CN115518653A (en) * | 2022-09-28 | 2022-12-27 | 北京化工大学 | Catalyst for efficiently catalyzing ethanol oxidative carbonylation to prepare diethyl carbonate and preparation method thereof |
-
2014
- 2014-10-15 CN CN201410555090.0A patent/CN104399498A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107262095A (en) * | 2017-07-20 | 2017-10-20 | 太原理工大学 | The preparation method of Copper-cladding Aluminum Bar graphen catalyst |
| CN115518653A (en) * | 2022-09-28 | 2022-12-27 | 北京化工大学 | Catalyst for efficiently catalyzing ethanol oxidative carbonylation to prepare diethyl carbonate and preparation method thereof |
| CN115518653B (en) * | 2022-09-28 | 2024-03-26 | 北京化工大学 | Catalyst for preparing diethyl carbonate by efficiently catalyzing ethanol to oxidize and carbonylate and preparation method thereof |
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Application publication date: 20150311 |