CN103012075B - 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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- CN103012075B CN103012075B CN201210543522.7A CN201210543522A CN103012075B CN 103012075 B CN103012075 B CN 103012075B CN 201210543522 A CN201210543522 A CN 201210543522A CN 103012075 B CN103012075 B CN 103012075B
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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 is prepared 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 subject to Domestic Resources supportability and environmental capacity restriction and global energy safety and reply climate change effect, resource environment constraint strengthening 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 atmosphere
2content increases year by year.CO in air
2the growth of content, causes temperature of the earth that change has occurred, and has become a serious global environmental problem.How to explore and effectively control CO in atmosphere
2content, caused the very big interest about multi-disciplinary research workers such as environment, material, chemistry.The method solving is exactly by CO
2effectively be converted into hydrocarbon fuel, due to CO
2be stable molecule, need provide energy by 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, the first step is first by CO
2synthesizing methanol, then obtains DME by methanol dehydration, and this respect has more research, and as far back as 1945, Ipatieff and Monroe have just reported CO on 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., wherein study at most with copper-based catalysts, and effect is best.Another kind of method is single stage method, by CO
2directly synthetic DME, methyl alcohol synthesizes and dehydration all completes in same step.Mao Dongsen etc. (ZL200810202011.2) adopt CuO-TiO
2-ZrO
2/ HZSM-5 is that (Industrial Catalysis, 2002,10 (2): 46-49) such as catalyzer, Liu Zhijian adopt CuO-ZnO-Al
2o
3/ HZSM-5, not good big etc. (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, Zeng 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 conventional high-temperature activation method easily causes the catalyst deactivation adding; Meanwhile, because carbon dioxide hydrogenation reaction is reversible reaction, be subject to the restriction of thermodynamic(al)equilibrium, the transformation efficiency of carbonic acid gas is only 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 analyzing known to carbonic acid gas catalyst system in differential responses, unoccupied orbital or electronics that the activation of carbonic acid gas need to match with its first ionization energy, can adopt complex metal compound with its orbital energy level of balance, provide coupling electronics with extra electric field or composite alloy, thereby activation carbonic acid gas, reaches the chemistry utilization of carbonic acid gas.CO
2activation method has multiple activation method, is exactly the most simply 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 state of material, mainly has high chemically active particle by atom, molecule, ion, electronics and free radical etc. and forms.Conventionally 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 is still normal temperature, can realize the reaction that cannot realize at normal temperatures by plasma body like this.
A series of research shows, plasma body is to CO
2there is good 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 as 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 +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 is mainly synthetic gas, and the product of silent discharge is except synthetic gas, also have hydro carbons and oxycompound.These plasma-activated CO
2research mainly for the preparation of methyl alcohol, synthetic gas etc., not for the synthesis of in 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 is prepared 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:
A kind of method that plasma-catalytic carbonic acid gas is prepared dme is with CO
2for raw material, using plasma activation CO
2after, carry out shortening dimethyl ether synthesis, operation steps is as follows:
1) plasma-activated CO
2:
CO
2be 5～14kV by a voltage, the dielectric barrier discharge plasma activating apparatus that frequency is 1～12kHz, an electrode of this device is pin electrode, another electrode is plate electrode with holes, CO
2be activated by the dielectric barrier discharge plasma district forming between pin-plate electrode after pin electrode.Then entering fixed-bed reactor reacts.
2) CO
2shortening is dme
The CO being activated
2enter after fixed-bed reactor, take Cu-Fe-Zr/HZSM-5 as catalyzer, by 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 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 compared with prior art, has advantages of following:
1. using plasma activation CO of the present invention
2, and directly by CO
2pass into reactor and carry out 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, easy and simple to handle, and speed of reaction is fast.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but it should be noted 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 forming between pin-plate electrode after pin electrode, then enter fixed-bed reactor and react.
2) CO
2shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes 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, then by the CO being 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 the condition of 240 ℃.The experimental result that employing the method is prepared dme is in 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 forming between pin-plate electrode after pin electrode, then enter fixed-bed reactor and react.
2) CO
2shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes 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, then by the CO being 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 the condition of 220 ℃.The experimental result that employing the method is prepared dme is in 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 forming between pin-plate electrode after pin electrode, then enter fixed-bed reactor and react.
2) CO
2shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes 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, then by the CO being 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 the condition of 260 ℃.The experimental result that employing the method is prepared dme is in 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 forming between pin-plate electrode after pin electrode, then enter fixed-bed reactor and react.
2) CO
2shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes 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, then by the CO being 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 the condition of 240 ℃.The experimental result that employing the method is prepared dme is in 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 forming between pin-plate electrode after pin electrode, then enter fixed-bed reactor and react.
2) CO
2shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes 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, then by the CO being 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 the condition of 240 ℃.The experimental result that employing the method is prepared dme is in 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 forming between pin-plate electrode after pin electrode, then enter fixed-bed reactor and react.
2) CO
2shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes 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, then by the CO being 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 the condition of 260 ℃.The experimental result that employing the method is prepared dme is in 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 forming between pin-plate electrode after pin electrode, then enter fixed-bed reactor and react.
2) CO
2shortening is dme
The Cu-Fe-Zr/HZSM-5 catalyzer that takes 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, then by the CO being 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 the condition of 280 ℃.The experimental result that employing the method is prepared dme is in table 1.
Table 1 experimental result
Note: 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 (1)
1. plasma-activated carbonic acid gas is prepared a method for dme, it is characterized in that, with CO
2for raw material, using plasma activation CO
2after, carry out shortening dimethyl ether synthesis, operation steps is as follows:
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 forming between pin-plate electrode after pin electrode, then enter fixed-bed reactor and react;
2) CO
2shortening is dme:
The Cu-Fe-Zr/HZSM-5 catalyzer that takes 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, then by the CO being 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 the condition of 240 ℃.
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| CN106890565B (en) * | 2017-03-28 | 2020-03-13 | 广西大学 | Method for converting carbon dioxide |
Citations (1)
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| 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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Non-Patent Citations (2)
| Title |
|---|
| Zr促进的Cu-ZnO/HZSM-5合成二甲醚催化剂的制备;王继元等;《石油炼制与化工》;20041231;第35卷(第12期);第13-17页 * |
| 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》.2004,第35卷(第12期),第13-17页. |
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