CN103012075A - Method for preparing dimethyl ether through activating carbon dioxide by using plasmas - Google Patents
Method for preparing dimethyl ether through activating carbon dioxide by using plasmas Download PDFInfo
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- CN103012075A CN103012075A CN2012105435227A CN201210543522A CN103012075A CN 103012075 A CN103012075 A CN 103012075A CN 2012105435227 A CN2012105435227 A CN 2012105435227A CN 201210543522 A CN201210543522 A CN 201210543522A CN 103012075 A CN103012075 A CN 103012075A
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Abstract
The invention discloses a method for preparing dimethyl ether through activating carbon dioxide by using plasmas. The method comprises the steps of taking the carbon dioxide as the raw material, carrying out gas-solid catalytic reaction on the CO2 by adopting a dielectric barrier discharge plasma activation device with the voltage of 5-14kV and the frequency of 0.05-12kHz and taking Cu-Fe-Zr/HZSM (Hydro Zeolite Socony Mobil)-5 and the like as catalysts in a fixed bed reactor with the temperature control under the conditions that the feed gas is a mixed gas of CO2 and H2 in the volume ratio of 1:2-1:5, the reaction gas hourly space velocity is 1000-5000h-1, the reaction pressure is 2-5MPa, the reaction temperature is 220-280 DEG C and the like, wherein the main reaction product is the dimethyl ether and the byproducts are methane, carbon monoxide and the like. The method disclosed by the invention has the advantages that the process and the operation are simple; the reaction rate is high; the CO2 conversion rate is high; the reaction process is green; and the selectivity and the yield of the dimethyl ether are high.
Description
Technical field
The invention belongs to the comprehensive utilization field of carbonic acid gas.Specifically a kind of plasma-catalytic carbonic acid gas prepares the method for dme.
Background technology
In recent decades, along with industrialization, Development of China's Urbanization are accelerated and the lasting upgrading of consumption structure, China's energy demand is rigidity and increases, be subjected to the restriction of Domestic Resources supportability and environmental capacity and global energy safety and reply climate change effect, the resource environment constraint is strengthened increasingly, " 12 " energy-saving and emission-reduction in period situation is still very severe, and task is very arduous.The CO that the hydrocarbon fuel combustions such as coal, oil, Sweet natural gas produce
2, considerably beyond level in the past, make the CO in the atmosphere
2Content increases year by year.CO in the air
2The growth of content causes temperature of the earth that change has occured, and has become a serious global environmental problem.How to explore and effectively control CO in the atmosphere
2Content, caused the multi-disciplinary research workers' such as relevant environment, material, chemistry very big interest.Solution is exactly with CO
2Effectively be converted into hydrocarbon fuel, because CO
2Be stable molecule, need provide energy with its conversion, study at present CO
2Path for transformation mainly contain: thermochemistry conversion, electrochemical conversion and photocatalytic conversion.
The synthetic DME of hydrogenation of carbon dioxide is that the synthetic DME of raw material is similar with adopting synthetic gas, and main method has two classes, two step method and single stage method.Two step method, namely the first step is first with CO
2Then synthesizing methanol obtains DME with methanol dehydration, and this respect has more research, and as far back as 1945, Ipatieff and Monroe have just reported CO on the Cu-Al catalyzer
2The research of synthesizing methanol by hydrogenating.The CO that studies morely
2The catalyzer of synthesizing methanol by hydrogenating has raney copper catalyst, and carried noble metal catalysis and copper-based catalysts etc. are wherein studied at most with copper-based catalysts, and effect is best.Another kind of method namely is single stage method, namely by CO
2Directly synthesize DME, methyl alcohol synthesizes and dehydration is all finished in same step.Mao Dongsen etc. (ZL200810202011.2) adopt CuO-TiO
2-ZrO
2/ HZSM-5 is (Industrial Catalysis, 2002,10 (2): 46-49) adopt CuO-ZnO-Al such as catalyzer, Liu Zhijian
2O
3/ HZSM-5, good not big etc. (the chemical industry progress, 2009,28(8): 1365-1370) adopt CuO-ZnO-Al
2O
3-ZrO
2/ HZSM-5, Huang Youmei etc. (Journal of Molecular Catalysis, 1997,11(4): 297-300) adopt Cu-ZnO-ZrO
2/ HZSM-5, Ceng Chongyu etc. (Nanjing University of Technology's journal, 2004,26(3): 89-93) adopt C207 and HZSM-5 mixing dual-function catalyst one-step synthesis dme.But highly stable because of carbonic acid gas itself, its activation is an insoluble bottleneck problem all the time, and high-temperature activation method commonly used easily causes the catalyst deactivation that adds; Simultaneously, because carbon dioxide hydrogenation reaction is reversible reaction, be subjected to the restriction of thermodynamic(al)equilibrium, the transformation efficiency of carbonic acid gas only is 25%-30%, and the selectivity of dme is 40%-50%.
CO
2Be converted in the process of useful chemical, a maximum difficult problem is exactly CO
2Activation.By the catalyst system analysis is as can be known in differential responses to carbonic acid gas, unoccupied orbital or electronics that the activation of carbonic acid gas need to be complementary with its first ionization energy, can adopt complex metal compound with its orbital energy level of balance, provide the coupling electronics with extra electric field or composite alloy, thereby the activation carbonic acid gas reaches the chemistry utilization of carbonic acid gas.CO
2Activation method has multiple activation method, the most simply is exactly that high temperature is to CO
2Activate, easily cause catalyst deactivation but carry out high temperature, and then have influence on CO
2Transformation efficiency etc.Plasma body is the 4th attitude of material, mainly has high chemically active particle by atom, molecule, ion, electronics and free radical etc. and forms.Usually the plasma body of indication is low-temperature plasma, and in low-temperature plasma, the extranuclear electron of atom is activated fully, and its electronic temp is up to 10
4K, and nuclear temperature is very low, so the upper material of macroscopic view still be normal temperature, the reaction that can can't realize at normal temperatures by the plasma body realization like this.
A series of studies show that, plasma body is to CO
2Have preferably activation (Liu Changjun etc., FuelProcess Technology, 1999,58(2-3): 119-134).Venugopalan etc. (Topic in Current Chemistry, 1983,1-58) think under the effect of plasma body CO
2Can activate and be CO
2*, CO, O isoreactivity material; Dai Bin etc. (China Environmental Science, 1999,19(5): 410-412) infer under the effect of plasma body CO
2Can ionize by high-energy electron, dissociation reaction, and produce CO
2 +The isoreactivity material; (University Of Tianjin's journal such as Liu Changjun, 2002,35(1): 19-22) find to transform methane and carbon dioxide with silent discharge and corona discharge, obtain different products: the product of corona discharge reaction mainly is synthetic gas, and the product of silent discharge also has hydro carbons and oxycompound except synthetic gas.These plasma-activated CO
2Research mainly for the preparation of methyl alcohol, synthetic gas etc., not for the synthesis of in the dme.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, less energy-consumption, low cost, high yield, eco-friendly a kind of plasma-activated carbonic acid gas prepares the method for dme.And determine best CO
2Plasma activated processes and at CO
2Shortening is the application of dme process.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
The method that a kind of plasma-catalytic carbonic acid gas prepares dme is with CO
2Be raw material, using plasma activation CO
2After, carry out the shortening dimethyl ether synthesis, operation steps is as follows:
1) plasma-activated CO
2:
CO
2Be 5～14kV by a voltage, frequency is the dielectric barrier discharge plasma activating apparatus of 1～12kHz, and an electrode of this device is pin electrode, and another electrode is plate electrode with holes, CO
2Be activated by the dielectric barrier discharge plasma district that between pin-plate electrode, forms behind the pin electrode.Then entering fixed-bed reactor reacts.
2) CO
2Shortening is dme
The CO that is activated
2After entering fixed-bed reactor, take Cu-Fe-Zr/HZSM-5 as catalyzer, press CO
2/ H
2The ratio of (volume ratio)=1: 2～1: 5 passes into hydrogen, is 1000～5000h at reaction velocity
-1, reaction pressure is 2～5MPa, and temperature of reaction is to carry out gas-solid catalysis under the conditions such as 220～280 ℃, and the reaction primary product is dme, by-product methane, carbon monoxide etc.
The sparking voltage of above-mentioned steps 1 medium barrier discharge plasma is preferably 14kV, and calibration is 12kHz.
The present invention has advantages of following compared with prior art:
1. using plasma of the present invention activates CO
2, and directly with CO
2Pass into reactor and carry out the reacting phase ratio, under identical reaction conditions, CO
2Selectivity and the yield of transformation efficiency, dme higher.
2. technique of the present invention is simple, and is easy and simple to handle, and speed of reaction is fast.
Embodiment
The invention will be further described below in conjunction with embodiment, but need to prove that range of application of the present invention is not limited to these embodiment.
Embodiment 1
1) plasma-activated CO
2
CO
2Unstripped gas is by a dielectric barrier discharge plasma activating apparatus, and the voltage between pin-plate electrode is 7kV, and frequency is 6kHz, CO
2Be activated by the dielectric barrier discharge plasma district that between pin-plate electrode, forms behind the pin electrode, then enter fixed-bed reactor and react.
2) CO
2Shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes by weighing 1g is put into fixed-bed reactor, and the content of this catalyzer n (Cu)/n (Fe)=1.5: 1 and Zr is 2%wt, and the silica alumina ratio of HZSM-5 is 300, again with the CO that is activated
2Pass into fixed-bed reactor, and press CO
2/ H
2The ratio of (volume ratio)=1: 3 passes into hydrogen, is 2000h at reaction velocity
-1, reaction pressure is 3MPa, temperature of reaction is to carry out gas-solid catalysis under 240 ℃ the condition.The experimental result that adopts the method to prepare dme sees Table 1.
Embodiment 2
1) plasma-activated CO
2
CO
2Unstripped gas is by a dielectric barrier discharge plasma activating apparatus, and the voltage between pin-plate electrode is 7kV, and frequency is 6kHz, CO
2Be activated by the dielectric barrier discharge plasma district that between pin-plate electrode, forms behind the pin electrode, then enter fixed-bed reactor and react.
2) CO
2Shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes by weighing 1g is put into fixed-bed reactor, and the content of this catalyzer n (Cu)/n (Fe)=2:1 and Zr is 0.5%wt, and the silica alumina ratio of HZSM-5 is 300, again with the CO that is activated
2Pass into fixed-bed reactor, and press CO
2/ H
2The ratio of (volume ratio)=1: 2 passes into hydrogen, is 5000h at reaction velocity
-1, reaction pressure is 2MPa, temperature of reaction is to carry out gas-solid catalysis under 220 ℃ the condition.The experimental result that adopts the method to prepare dme sees Table 1.
Embodiment 3
1) plasma-activated CO
2
CO
2Unstripped gas is by a dielectric barrier discharge plasma activating apparatus, and the voltage between pin-plate electrode is 7kV, and frequency is 6kHz, CO
2Be activated by the dielectric barrier discharge plasma district that between pin-plate electrode, forms behind the pin electrode, then enter fixed-bed reactor and react.
2) CO
2Shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes by weighing 1g is put into fixed-bed reactor, and the content of this catalyzer n (Cu)/n (Fe)=1.5:1 and Zr is 2%wt, and the silica alumina ratio of HZSM-5 is 300, again with the CO that is activated
2Pass into fixed-bed reactor, and press CO
2/ H
2The ratio of (volume ratio)=1: 3 passes into hydrogen, is 3000h at reaction velocity
-1, reaction pressure is 3MPa, temperature of reaction is to carry out gas-solid catalysis under 260 ℃ the condition.The experimental result that adopts the method to prepare dme sees Table 1.
Embodiment 4
1) plasma-activated CO
2
CO
2Unstripped gas is by a dielectric barrier discharge plasma activating apparatus, and the voltage between pin-plate electrode is 14kV, and frequency is 12kHz, CO
2Be activated by the dielectric barrier discharge plasma district that between pin-plate electrode, forms behind the pin electrode, then enter fixed-bed reactor and react.
2) CO
2Shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes by weighing 1g is put into fixed-bed reactor, and the content of this catalyzer n (Cu)/n (Fe)=1.5:1 and Zr is 2%wt, and the silica alumina ratio of HZSM-5 is 300, again with the CO that is activated
2Pass into fixed-bed reactor, and press CO
2/ H
2The ratio of (volume ratio)=1: 3 passes into hydrogen, is 2000h at reaction velocity
-1, reaction pressure is 3MPa, temperature of reaction is to carry out gas-solid catalysis under 240 ℃ the condition.The experimental result that adopts the method to prepare dme sees Table 1.
Embodiment 5
1) plasma-activated CO
2
CO
2Unstripped gas is by a dielectric barrier discharge plasma activating apparatus, and the voltage between pin-plate electrode is 14kV, and frequency is 12kHz, CO
2Be activated by the dielectric barrier discharge plasma district that between pin-plate electrode, forms behind the pin electrode, then enter fixed-bed reactor and react.
2) CO
2Shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes by weighing 1g is put into fixed-bed reactor, and the content of this catalyzer n (Cu)/n (Fe)=2:1 and Zr is 0.5%wt, and the silica alumina ratio of HZSM-5 is 300, again with the CO that is activated
2Pass into fixed-bed reactor, and press CO
2/ H
2The ratio of (volume ratio)=1: 3 passes into hydrogen, is 2000h at reaction velocity
-1, reaction pressure is 3MPa, temperature of reaction is to carry out gas-solid catalysis under 240 ℃ the condition.The experimental result that adopts the method to prepare dme sees Table 1.
Embodiment 6
1) plasma-activated CO
2
CO
2Unstripped gas is by a dielectric barrier discharge plasma activating apparatus, and the voltage between pin-plate electrode is 14kV, and frequency is 12kHz, CO
2Be activated by the dielectric barrier discharge plasma district that between pin-plate electrode, forms behind the pin electrode, then enter fixed-bed reactor and react.
2) CO
2Shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes by weighing 1g is put into fixed-bed reactor, and the content of this catalyzer n (Cu)/n (Fe)=1.5:1 and Zr is 2%wt, and the silica alumina ratio of HZSM-5 is 300, again with the CO that is activated
2Pass into fixed-bed reactor, and press CO
2/ H
2The ratio of (volume ratio)=1: 3 passes into hydrogen, is 3000h at reaction velocity
-1, reaction pressure is 3MPa, temperature of reaction is to carry out gas-solid catalysis under 260 ℃ the condition.The experimental result that adopts the method to prepare dme sees Table 1.
Embodiment 7
1) plasma-activated CO
2
CO
2Unstripped gas is by a dielectric barrier discharge plasma activating apparatus, and the voltage between pin-plate electrode is 5kV, and frequency is 1kHz, CO
2Be activated by the dielectric barrier discharge plasma district that between pin-plate electrode, forms behind the pin electrode, then enter fixed-bed reactor and react.
2) CO
2Shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes by weighing 1g is put into fixed-bed reactor, and the content of this catalyzer n (Cu)/n (Fe)=1.5:1 and Zr is 2%wt, and the silica alumina ratio of HZSM-5 is 300, again with the CO that is activated
2Pass into fixed-bed reactor, and press CO
2/ H
2The ratio of (volume ratio)=1: 5 passes into hydrogen, is 1000h at reaction velocity
-1, reaction pressure is 5MPa, temperature of reaction is to carry out gas-solid catalysis under 280 ℃ the condition.The experimental result that adopts the method to prepare dme sees Table 1.
Table 1 experimental result
Annotate: X (CO
2): the transformation efficiency of carbonic acid gas, S (DME): the selectivity of dme, S (CO): the selectivity of carbon monoxide, S (CH
4): the selectivity of methane, Y (DME): the yield of dme.
Claims (3)
1. a plasma-activated carbonic acid gas prepares the method for dme, it is characterized in that, with CO
2Be raw material, using plasma activation CO
2After, carry out the shortening dimethyl ether synthesis, operation steps is as follows:
1) plasma-activated CO
2:
CO
2Be 5～14kV by a voltage, frequency is the dielectric barrier discharge plasma activating apparatus of 1～12kHz, and an electrode of this device is pin electrode, and another electrode is plate electrode with holes, CO
2Be activated by the dielectric barrier discharge plasma district that between pin-plate electrode, forms behind the pin electrode, then enter fixed-bed reactor and react, the CO that obtains being activated
2
2) CO
2Shortening is dme:
The CO that is activated
2After entering fixed-bed reactor, take Cu-Fe-Zr/HZSM-5 as catalyzer, CO by volume
2/ H
2=1: 2～1: 5 ratio passes into hydrogen, is 1000～5000h at reaction velocity
-1, reaction pressure is 2～5MPa, and temperature of reaction is to carry out gas-solid catalysis under the conditions such as 220～280 ℃, and the reaction primary product is dme, by-product methane, carbon monoxide.
2. plasma-activated carbonic acid gas according to claim 1 prepares the method for dme, it is characterized in that CO
2Before reaction through a plasma activated processes.
3. plasma-activated carbonic acid gas according to claim 1 prepares the method for dme, it is characterized in that the plasma-activated CO of described step 1)
2: CO wherein
2Be 14kV by a voltage, frequency is the dielectric barrier discharge plasma activating apparatus of 12kHz.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387243A (en) * | 2014-11-26 | 2015-03-04 | 广西大学 | Preparation method of dimethyl ether |
| CN106890565A (en) * | 2017-03-28 | 2017-06-27 | 广西大学 | A kind of method of carbon dioxide conversion |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101849036A (en) * | 2007-05-04 | 2010-09-29 | 原则能源解决方案公司 | Produce hydrocarbon by carbon source and hydrogen source |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101849036A (en) * | 2007-05-04 | 2010-09-29 | 原则能源解决方案公司 | Produce hydrocarbon by carbon source and hydrogen source |
Non-Patent Citations (1)
| Title |
|---|
| 王继元等: "Zr促进的Cu-ZnO/HZSM-5合成二甲醚催化剂的制备", 《石油炼制与化工》, vol. 35, no. 12, 31 December 2004 (2004-12-31), pages 13 - 17 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387243A (en) * | 2014-11-26 | 2015-03-04 | 广西大学 | Preparation method of dimethyl ether |
| CN104387243B (en) * | 2014-11-26 | 2016-01-27 | 广西大学 | A kind of preparation method of dme |
| CN106890565A (en) * | 2017-03-28 | 2017-06-27 | 广西大学 | A kind of method of carbon dioxide conversion |
| CN106890565B (en) * | 2017-03-28 | 2020-03-13 | 广西大学 | Method for converting carbon dioxide |
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