CN103796751A - Electronegative-ion-aided method and apparatus for synthesis of ethanol and organic compounds - Google Patents
Electronegative-ion-aided method and apparatus for synthesis of ethanol and organic compounds Download PDFInfo
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- CN103796751A CN103796751A CN201280040307.3A CN201280040307A CN103796751A CN 103796751 A CN103796751 A CN 103796751A CN 201280040307 A CN201280040307 A CN 201280040307A CN 103796751 A CN103796751 A CN 103796751A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 39
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 150000002500 ions Chemical class 0.000 claims abstract description 53
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 31
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 239000011630 iodine Substances 0.000 claims abstract description 8
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 239000004202 carbamide Substances 0.000 claims abstract description 5
- JOHCVVJGGSABQY-UHFFFAOYSA-N carbon tetraiodide Chemical compound IC(I)(I)I JOHCVVJGGSABQY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- 150000001450 anions Chemical class 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000009616 inductively coupled plasma Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- 206010003645 Atopy Diseases 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 90
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001868 water Inorganic materials 0.000 abstract description 18
- 235000006408 oxalic acid Nutrition 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229960004424 carbon dioxide Drugs 0.000 description 25
- 239000000047 product Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- -1 ethanol Chemical class 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 206010034432 Performance fear Diseases 0.000 description 2
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- 150000001768 cations Chemical class 0.000 description 2
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- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SISAYUDTHCIGLM-UHFFFAOYSA-N bromine dioxide Inorganic materials O=Br=O SISAYUDTHCIGLM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- WXDJHDMIIZKXSK-UHFFFAOYSA-N iodine dioxide Inorganic materials O=I=O WXDJHDMIIZKXSK-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
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Abstract
Provided are electronegative-ion-aided methods and apparatus to achieve reduction of carbon dioxide gas into useful products. In one embodiment, using different methods of discharge, the electronegative gases forms non-equilibrium electronegative ions, so that carbon dioxide reduction occurs for the production of organic compounds. When carbon dioxide is introduced into the container containing at least one electronegative gas, such as water, ammonia, bromine or iodine vapor, it reacts to form organic compounds, such as ethanol, methanol, and oxalic acid in the case of water, urea in the case of ammonia, and tetraiodomethane in the case of iodine.
Description
The cross reference of related application
The application require within on 08 19th, 2011, submit to the 61/575th, the priority that No. 201110268283.4th, the Chinese patent application submitted in No. 264 U.S. Provisional Applications and on September 28th, 2011, and it is included in herein as a reference in full.
Technical field
The present invention discloses a kind of ethanol and organic compound synthetic method and equipment,, under the electron discharge conditions such as negative corona, makes electronegative gas, as steam and carbon dioxide etc., forms ethanol and other organic compound.In instantiation, Electronic Negative corona discharge forms electronegative gas ion, and as anion or active groups such as steam anion, carbon dioxide, this material is from various initial gas, as the OH under at high energy conditions
-.Electronegative gas ion and electroneutral gas molecule react, and generate ethanol or other organic compounds.Apparatus of the present invention comprise a reaction vessel, at least have an electrode and a high voltage source, produce negative corona in order to the top at electrode.The electronegative gas ion that negative corona region in container generates, with nonpolar molecule (as, electroneutral molecule) or react without the gas molecule of additional electron, forms ethanol and other organic compound.
Background technology
Carbon dioxide (CO
2) efficient Collection and use problem be that the energy produces and one of the ultimate challenge in energy storage field.In order effectively to utilize or minimizing CO
2discharge, finds feasible CO from production source (as waste gas)
2utilize technology most important, also therefore carried out many research work.Waste gas normally air pressure is about the moderate temperature gas of atmospheric gas pressure.Therefore, for the extensive CO that reduces
2discharge, effectively utilizes and reduces waste gas and neutralize the CO in some large-scale production sources
2just seem particularly important.In greenhouse gases, main component carbon dioxide is mainly the product forming after fossil fuel and organic compound burning, accounts for 2/3rds of greenhouse gases.[1-3]
At present, tend in the world regard carbon dioxide as cheap resource material, adopt chemical method to be translated into large industrial chemicals, thereby realize the target turning waste into wealth.But carbon dioxide is a kind of extremely stable gas, under normal temperature and pressure conditions, process very difficult.And the previous method for chemical recycling of carbon dioxide generally must could realize under higher temperature and pressure, this has just increased processing cost, also has potential safety hazard simultaneously.At present, for synthetic useful compound, be mainly used in the research of carbon dioxide plasma decomposes and restructuring just on stream.[4-6]
At present, electronegative gas has been subject to extensive concern, and the focus of concern mainly concentrates in surface treatment, atmospheric science, waste gas purification Environmental Studies and other related application.Therefore, in contemporary plasma physics, anion all plays very important effect under many circumstances, thereby also the fundamental property of anion has been done to large quantity research.[7-9]
The present invention utilizes plasma source electron gain, produces electronegative gas ion, for example, in order to being useful chemical substance, ethanol by carbon dioxide conversion.In instantiation, around electrode, form negative corona, produce required electronics.The electrode of high negative potential is by negative corona course of reaction, and generation current in one or more electronegative gases (as water vapour) then, by adhering to gas, forms electronegative gas around electrode.Electrode shape is aciculiform or linear, top band cusp.When potential gradient develops into enough greatly in electrode tip, so that during to gas electron emission, the gas at this place will be adhered to by extra electron, or negative electricity ionization, forms electronegativity ion.If electrical body is with cusp, the gradient of this cusp ambient gas can be more much higher than other places so.Finally, the electronegativity ion producing is the adjacent domain to low potential by charge transfer, or restructuring forms gas molecule.
For the most possible metal using in corona discharge assembly, be approximately 4eV~5eV from corona electrode surface removal electron institute energy requirement.Electrode may be made up of nickel, copper, silver, iron, steel, tungsten, carbon or platinum.The present invention does not make specific limited to the type of electrode material, and any material can form negative corona, all can use about the electronics of 4eV~5eV with produce power.Therefore the electric discharge electronics that energy is 4eV~5eV can be attached to the low speed electronegative gas molecule of kinetic energy lower (25 ℃ time be about 3/2kT or 0.038eV), shift energy, thereby form the high speed anion having compared with kinetic energy.In addition, owing to having additional charge on electronegative gas ion, so the potential energy of anion likely can be higher.In anion total can higher than in original molecule total can, thereby cause H
2o anion and CO
2there is strong collision, produce enough energy for H
2o
-and CO
2between reaction, thereby shape organic molecule, as ethanol.
The present invention does not do specific limited to the type of device.However, we think, gas-phase reaction system uses electronegative gas, produces electronegative gas ion by electron attachment negative corona.When extra electron is attached to while forming electronegative group on gas molecule, owing to producing corona discharge, thereby on the electronics adhering to, just form charged anion and the charged group of energy at 4eV~5eV.The lower electroneutral gas molecule of the electronegative gas ion that these energy are higher and energy is (as CO
2) react, be formed with organic compounds (as ethanol), thereby can reach minimum.
If by using gas to fail to form electronegativity ion, the molecule that the electronics of speed can only be larger with quality bumps, thereby the energy of electronics (as 4eV~5eV) is transferred to gas molecule.For forming cation and electronics, these energy possibly than the ionization energy of this nonpolar molecule (as 12.6eV(CH
4)) much less, carry out reforming reaction required under activated atmos environment (atmospheric temperature and pressure) (with CO therefore lack enough energy
2react).Therefore, because nonpolar molecule is not with electronegativity gas ion, so cannot form anion, energy also cannot be delivered to all molecules effectively, thereby reduce the possibility of activating reaction thing, caused cannot completing goal response under atmospheric environment (atmospheric temperature and pressure).
Therefore, adopt the method for electronegative gas ion to have the following advantages: the energy of electronegative gas Ions Absorption is from negative corona electronics, and whole process is in lower temperature, pressure environment, so, just can avoid adopting the method under high-temperature and high-pressure conditions, save consequent expense, also reduced difficulty simultaneously.In addition, the just description of following correlative technology field, other advantages that the electronegative gas ion method that the present invention adopts and equipment have are also apparent.
Summary of the invention
One aspect of the present invention is provided for synthesizing alcohol or from CO
2extract the method for other organic compounds; One or more electronegative gases (as steam, ammonia, bromine, iodine and carbon dioxide) are exposed in electron source, to form electronegative gas ion.Electron source can be a kind of typical plasma source, can produce cation and anion.In an instantiation, negative corona is for generation of electronegativity gas ion source.In this case, one or more electronegative gases are exposed under negative corona discharge environment, and electron attachment is on gas molecule, to form electronegative gas ion.Be attached to electronegative gas Ions Absorption on electronics from the energy of electronics, therefore there is higher energy.Usually, the energy that electronegative gas ion absorbs from electronics is between 4eV~5eV.Electronegative gas ion and CO that energy is higher
2react, generate organic compound, as ethanol, methyl alcohol, urea, oxalic acid and tetraiodo methane.Synthetic organic compound can be used as fuel or prepares the raw material of industry of other chemicals.
On the other hand, adopt reaction vessel to implement method as herein described.Reaction vessel comprises shell, contains the multiple electrodes that are attached to container both sides on shell.High voltage source provides a negative electrical charge for electrode.Each electrode generates a negative corona, and the extra electron that can be attached on electronegative gas is provided.Adopt multiple air inlets by CO
2be filled with container with electronegative gas, adopt exhaust outlet that bubbing is shifted out to reaction vessel.As required, container can comprise one or more magnet, with the region that attracts electronegative gas ion and produce electronegative gas ion high concentration.
This method and equipment utilization electronegative gas ion and CO
2bring out reaction, make CO
2reduction, final anthropogenics.Under normal pressure, any catalyst be need not use, electronegative gas ion and the CO such as steam, iodine gas, bromine gas or ammonia made
2react, get final product synthesizing alcohol, methyl alcohol, oxalic acid, tetraiodo methane, urea or other compounds.
Other targets of the present invention and advantage will be described in detail in specific embodiments later.
Accompanying drawing explanation
Fig. 1 is for for generating electronegative gas ion and from CO
2the schematic diagram of the embodiment of the reaction vessel of anthropogenics.
Fig. 2 has shown from CO
2and H
2o manufactures the flow chart of the embodiment of the facility of ethanol.
Specific embodiments
Describe herein and claim in the term " electronegative gas " that adopts refer to that its atom and molecule can form the gas of anion by the adhering to of extra electron.Herein the implication of other technologies and scientific terminology all with operate similar techniques, to have the common understanding of the horizontal personnel of general technology identical.
In the embodiment of the inventive method, the reaction vessel adopting comprises that at least one can form the electrode of plasma or negative corona.Plasma or negative corona must have sufficiently high energy provides electronics, thereby by CO
2be converted into required organic product.Below having described the present invention adopts electrode that an embodiment of negative corona is provided.It should be noted that the present invention is not limited thereto, if conventional plasma discharge can occur electrode under sufficiently high energy state, and generate electronics, this electrode also can be used for the present invention so.
By one or more admission line, by electronegative gas and CO
2be filled with reaction vessel.In the time synthesizing as organic compounds such as ethanol, can adopt steam as electronegative gas.In reaction vessel, be filled with iodine gas, bromine gas, ammonia and CO
2can synthesize other organic compounds.Can adopt batch or continuous operation mode, although continuous operation mode is more suitable for the product building-up process of larger amt.
In reaction vessel, put into multiple electrodes to produce the negative corona electric field of electrode surrounding.In certain embodiments, electrode is linear or aciculiform element, has a cusp at eletrode tip.Tip can be the most advanced and sophisticated high negative charge region of next-door neighbour track is provided.Can use the electrode or the nickel coating electrode that are formed by nickel, copper, silver, iron, steel, tungsten, carbon or platinum.The present invention is not limited to the electrode material of particular type, thereby the material of any electronics that forms the about 4eV~5eV of negative corona generation energy all can use.
Adopt high voltage source to the electrifying electrodes in container, the tip place of electrode can form negative corona.In the corona of eletrode tip, can generate the electronics that energy is 4eV~5eV.The electronics adhering near electronegative gas molecule (as steam) electrode can generate high energy gas ion.High energy gas ion and other gas molecules mutually collide and have an effect in container, thereby synthesize various products what follows.
Conventionally under normal pressure or the air pressure a little more than normal pressure, reaction vessel is operated.Reaction vessel planted agent keeps being applicable to electronegative gas and product and reduces required temperature.Generally speaking, the temperature of container should be between normal temperature and 100 ℃.For example, in the time adopting steam as electronegative gas, for avoiding the steam in container to condense in inwall or other places of reaction vessel, the temperature in reaction vessel should be up to 100 ℃.Can adopt following any one mode: the temperature in container is remained on below 100 ℃, prevent condensing of steam by heating container wall; Or inject excessive steam in container, to keep sufficient vaporous water steam.In the time that the product generating is ethanol, the temperature of container need remain on 75 ℃ of left and right, and for the ethanol that approaches boiling point, temperature should remain on 78 ℃ of left and right.
Reaction vessel should comprise the magnet being arranged in container, to attract electronegative gas ion and to form the region that gas ion is more intensive.Can increase like this probability that gas ion and other gas molecules collide mutually, thus initiation reaction.In the time that generation has the electronegative gas ion of higher-energy and stronger reducing power, these gas ions can with carbon dioxide generation reduction reaction, generate as required organic products such as ethanol.
Although the present invention is not limited to specific reaction mechanism, inventors still think, electronics and gas ion mutually adhere in corona, and produce power reacts electronegative gas ion and carbon dioxide.As long as the gas ion gross energy obtaining from negative corona electron attachment is greater than the Gibbs free energy difference of given gas reaction, just can further promote reduction process, obtain required organic product.For example, generating by following reaction (4) in the process of ethanol, need the steam ion of three moles.Each steam ion obtains the energy of about 5eV or 482.5 kj/mol and then driving a reaction process from the electronics adhering to.In the course of reaction of formation ethanol, the steam ion of three moles can provide the energy of 1447.35 kj/mol, and this is higher than the energy of required available 1306.1 kilojoules of Gibbs free energy of reaction.
Following description is to the various ions that formed by electronics under corona discharge condition, and in reaction vessel, the interaction of gas ion and neutral gas molecule is set forth.Under corona discharge condition, may there is the interaction of two types in carbon dioxide and electronics.
co
2+e
-→CO+1/2O
2+e
- (1)
CO
2anion can react with neutral gas molecule what follows, thereby is formed with organic compounds.
Although water vapour molecule is due to the sealing of its electronic shell and do not have electron affinity, under corona discharge condition, steam has powerful attraction polarization to extra electron, can be in conjunction with extra electron, and release energy.Can estimate, under negative corona discharge condition, steam can obtain extra electron, forms H
2o
-.
According to process of the present invention, at normal pressure, 50 ℃~150 ℃ time, use water vapour and CO
2gas is to generate ethanol.In the ethanol forming, contain a small amount of methyl alcohol, perhaps also have Microamounts of Oxalic Acid as accessory substance.May form carbonic anhydride ion as above.The forming process of corona discharge Water Under steam ion is as follows:
H
zO+e
-→H
2O
- (3)
Water vapour ion and carbonic anhydride ion can react with neutral gas molecule in reactor, form ethanol.It is believed that CO
2the reaction mechanism that is converted into ethanol is as follows:
3H
2O
-+2CO→C
2H
5OH+20
2+3e
- (4)
3H
2O
-+2CO
2→C
2H
5OH+3O
2+3e
- (5)
The forming process of methyl alcohol in reactor is as follows:
4H
2O
-+ZCO
2→2CH
3OH+3O
2+4e
- (7)
2H
2O
-+CO→CH
3OH+O
2+2e
- (8)
The forming process of oxalic acid in reactor is as follows:
Ammonia is a kind of electronegative gas, can, under corona discharge condition, adhere to electronics by following reactive absorption:
Ammonium ion can occur to react as follows with carbon dioxide or carbon monoxide in reactor, forms urea:
Iodine is also a kind of electronegative gas, can under corona discharge condition, form anion, when temperature is 70 ℃, can in carbon dioxide, successfully synthesize tetraiodo methane, and conversion ratio is up to 88%, and step is as follows:
According to the difference of required product, in the time carrying out method provided by the present invention, also can adopt other electronegative gases, for example chlorine or bromine.
There is enough energy by CO
2other electronics sources that are converted into organic products, also can be used for the inventive method.Electronegative gas ion also can produce by ion gun non-thermal by other or heat plasma technology or anion, comprise high-frequency method, for example radio frequency plasma (RF), microwave plasma, inductively coupled plasma (ICP), and high voltage method, for example dielectric barrier discharge (DBD) and electron beam (EB).Any generation has enough energy and CO
2the method of the electronegative gas ion reacting, all can be used for the inventive method.
Fig. 1 is shown in by the schematic diagram of synthesizing alcohol or other reactive organic molecule device embodiment, and reactor 100 contains a shell 111, and shell can be steel, stainless steel or any other applicable material.Because reaction is under atmospheric pressure or approach very much under atmospheric pressure and carry out, so the thickness of shell can be low to moderate 1/4 inch.
Can insert in the enclosure lining 117, reduce shell of reactor the possibility shocking by electricity occurs.Lining 117 can be nickel or other applicable material.If necessary, between inside and outside shell, can add insulating materials, or adopt appropriate device to heat inner casing, reduce water vapour or product and condense, heater can be steam jacket heating.
Negative high voltage power source (not shown) is connected with multiple electrodes 116.In an embodiment, negative high voltage power source at least provides the voltage of 1 kilovolt.The selection of voltage (intensity) should meet the following conditions, that is, make the electronegative gas that is delivered to reactor in the ionization of the interior energy quilt of reative cell 118 height.
In operating process, in the time that electrode 116 is subject to negative high voltage power source excitation, eletrode tip forms negative corona, then forms negative electricity and has stage fright.Electronegative gas, as water vapour, is delivered to reactor by air inlet 113.Water vapour enters reative cell, is exposed to the negative electricity that eletrode tip produces and has stage fright.Charged electron attachment in corona, in hydrone, forms electronegativity water ion.
Carbon dioxide is delivered to reactor by air inlet 113, and partial CO 2 molecule can adsorb charged electronics at corona field, thereby forms electronegative carbon dioxide molecule.Charged water vapour/carbonic anhydride ion and neutral water steam/carbon dioxide molecule react, and form ethanol.In the time that vessel temp remains on more than 78 ℃, alcohol vapour, together with byproduct of reaction, part water vapour and CO
2together, discharge by exhaust outlet 110.If product is liquid form, can add a blast pipe at reactor bottom, for collecting reaction product.
In an embodiment, cylinder 112 is in the reactor containing bar magnet or magnetic bead.Cylinder 112 can be made up of wire netting, as nickel screen, nickel sponge, platinum guaze or Graphene, so that bar magnet or the magnetic bead of absorption the inside.Bar magnet or magnetic bead produce magnetic field around cylinder 112, attract electronegative water vapour ion and carbonic anhydride ion, thereby form a dense gas ions, and cylinder 112 can be supported by the stay pipe 115 in container.The flow chart of exemplary ethanol production facilities is shown in Fig. 2, and steam generator 210, by the first air inlet 214, is delivered to reactor 212 by water vapour.Carbon dioxide source 216, by the second air inlet 218, is delivered to reactor 212 by carbon dioxide.When liquid state or solid carbon dioxide source of the gas are during as source of the gas, should adopt control conversion equipment.
Water vapour is ionized in reactor, while and CO
2react, form ethanol as above.Ethanol product, with accessory substances such as water vapour and methyl alcohol, oxalic acid, is discharged reactor by exhaust outlet 220, is then transported in condenser 222, is condensed into liquid, then is transported to distilling apparatus 224 from condenser 222, carries out the isolation and purification of ethanol.From distilling apparatus product out, its ethanol content can be up to 95%.
If necessary, can be delivered to ultrafiltration apparatus 226 from distilling apparatus product out, form final ethanol product.
In view of those of ordinary skill in the art can understand methods described herein, therefore the above embodiment of the present invention and other embodiment are all variable and revise, but can not exceed the limited range of claims.Therefore, detailed description of preferred embodiment should be illustrative, and non-limiting.
List of references
All publications mentioned in this article and patent, comprise following Listed Items, all include in herein as a reference in full, as each independent publication or patent application by especially be hereby incorporated by individually the same.If any conflict, be as the criterion with present patent application (comprising all definition herein).
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Claims (18)
1. a method that is organic compound by carbon dioxide conversion, said method comprising the steps of:
In the container with at least one electrode, mix at least one electronegative gas and carbon dioxide;
Described at least one electrode is applied to negative voltage, thereby produce negative corona discharge with the tip at described electrode, thereby generate electronegativity ion, it is organic compound that the energy of described electronegativity ion is enough to described carbon dioxide conversion.
2. method according to claim 1, wherein, the group that described electronegative gas selects free steam, ammonia, iodine gas, bromine gas, chlorine and constitutes.
3. method according to claim 1, wherein, described electronegative gas is steam, and described organic compound is ethanol.
4. method according to claim 1, wherein, described electronegative gas is ammonia, and described organic compound is urea.
5. method according to claim 1, wherein, described electronegative gas is iodine gas, described organic compound is tetraiodo methane.
6. an equipment that is organic compound by carbon dioxide conversion, described equipment comprises:
Inner casing, described inner casing is defined as reaction vessel in shell;
At least one electrode, described electrode is fixedly connected on described shell, and the tip of described electrode is stretched in described reaction vessel;
At least one air supply pipe, described air supply pipe provides unstripped gas to described reaction vessel; And
Efferent duct, product is shifted out described reaction vessel by described efferent duct.
7. equipment according to claim 6, described equipment also comprises multiple electrodes, described electrode is fixedly connected on described shell, and stretches in described reaction vessel.
8. equipment according to claim 7, wherein, described electrode is the shape of pin or line.
9. equipment according to claim 8, wherein, described electrode is made up of metal, and described metal selects the group of free nickel, copper, silver, iron, steel, tungsten or platinum composition.
10. equipment according to claim 8, wherein, described electrode is made up of carbon.
11. equipment according to claim 9, wherein, described electrode is coated with atopic catalysis material.
12. equipment according to claim 11, wherein, described electrode is coated with catalyst, the group that described catalyst selects free nickel, rhodium, cobalt, phosphorus, caesium and platinum to form.
13. equipment according to claim 9, described equipment is also included in the unit that brings out magnetic field in described reaction vessel.
14. equipment according to claim 9, described equipment also comprises the metal column being fixed in described reaction vessel, and wherein, described metal cylinder comprises multiple bar magnets or magnetic bead.
15. equipment according to claim 14, wherein, described metal cylinder is wire netting.
16. equipment according to claim 15, the group that described wire netting selects free nickel screen, is coated with the copper mesh of catalyst, the nickel screen of the nickel screen of sponge nickel parcel and graphite parcel forms.
17. 1 kinds of methods that are organic compound by carbon dioxide conversion, said method comprising the steps of:
In the container with at least one electron source, mix at least one electronegative gas and carbon dioxide, described electron source is used to form anion; And
In described container, produce electron discharge by described electron source, thereby generate electronegativity ion, it is organic compound that the energy of described electronegativity ion is enough to described carbon dioxide conversion.
18. methods according to claim 17, wherein, described electron source selects the group that free radio frequency plasma (RF), microwave plasma, inductively coupled plasma (ICP), dielectric obstacle electric discharge (DBD) and electron beam (EB) form.
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CN2011102682834 | 2011-09-28 | ||
CN2011102682834A CN102993053A (en) | 2011-09-28 | 2011-09-28 | Electronegative plasma assisted carbon dioxide emission reduction processing method and device thereof |
PCT/US2012/051472 WO2013028568A1 (en) | 2011-08-19 | 2012-08-17 | Electronegative-ion-aided method and apparatus for synthesis of ethanol and organic compounds |
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WO2021142919A1 (en) * | 2020-01-17 | 2021-07-22 | 西安交通大学 | Plasma-based carbon fixation system and carbon fixation method |
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