CN103796751B - 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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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
Cross reference to related applications
This application claims No. 61/575,264 U.S. Provisional Application submitted to on 08 19th, 2011 and September 28 in 2011
The priority of the Chinese patent application the 201110268283.4th that day submits to, and it is hereby incorporated by full reference.
Technical field
The present invention discloses a kind of ethanol and organic compound synthetic method and equipment, that is, in the electron discharge condition such as negative corona
Under, make electronegative gas, such as vapor and carbon dioxide etc., form ethanol and other organic compound.In instantiation, electricity
Sub- negative corona discharge forms electronegative gas ion, such as the anion such as vapor anion, carbon dioxide or active group, should
Material is derived from various initial gas, the such as OH under high energy conditions-.Electronegative gas ion and electric neutrality gas molecule occur anti-
Should, generate ethanol or other organic compound.Apparatus of the present invention include a reaction vessel, at least have an electrode and one
High voltage power supply, in order to produce negative corona on the top of electrode.The electronegative gas ion of the negative corona Area generation in container,
With nonpolar molecule(As electric neutrality molecule)Or the gas molecule of no additional electron reacts, form ethanol and other is organic
Compound.
Background technology
Carbon dioxide(CO2)Efficient collection and Utilizing question be the energy produce and energy storage field one of ultimate challenge.
For effectively utilizes or minimizing CO2Discharge, from the source of production(In waste gas)Find feasible CO2Most important using technology, also because
This has carried out many research work.Waste gas is typically the moderate temperature gas that air pressure is about atmospheric gas pressure.Therefore, in order to extensive
Reduce CO2Discharge, effectively utilizes and reduces waste gas and neutralize the CO in some large-scale production sources2Just it is particularly important.Greenhouse gas
The product that in body, main component carbon dioxide is formed after being mainly Fossil fuel and organic compound burning, accounts for greenhouse gases
2/3rds.[1-3]
At present, tend in the world regard carbon dioxide as cheap resource material, be translated into using chemical method
Large industrial chemicals, thus realize the target turning waste into wealth.But, carbon dioxide is a kind of extremely stable gas, in room temperature
Process extremely difficult under condition of normal pressure.And the previous method for chemical recycling of carbon dioxide typically must be in higher temperature and pressure
Lower just enable, this adds increased processing cost, also there is potential safety hazard simultaneously.At present, in order to synthesize useful compound, main
Be used for carbon dioxide plasma decompose and restructuring research just on stream.[4-6]
At present, electronegative gas receives significant attention, focus of attention be concentrated mainly on surface treatment, atmospheric science,
In waste gas purification environmental studies and other related application.Therefore, in contemporary plasma physics, anion is in a lot of situations
Under all play very important effect, thus also numerous studies have been done to the fundamental property of anion.[7-9]
The present invention utilizes plasma source to obtain electronics, produces electronegative gas ion, in order to by carbon dioxide conversion
For useful chemical substance, such as ethanol.In instantiation, form negative corona in surrounding them, produce required electronics.High negative
The electrode of current potential passes through negative corona course of reaction, in one or more electronegative gas(As water vapour)Middle generation electric current, then
By adhering to gas, form electronegative gas in surrounding them.Electrode shape is in aciculiform or linear, top band cusp.Work as potential
Gradient develops into sufficiently large in electrode tip, so that during to gaseous emission electronics, the gas at this will be adhered to by extra electron,
Or negative electricity ionization, form electronegativity ion.If electrical body carries cusp, then the gradient of this cusp ambient gas can be than it
His place is much higher.Finally, produced electronegativity ion is by the adjacent domain of charge transfer to low potential, or restructuring forms gas
Body molecule.
For the metal using most possible in corona discharge assembly, energy needed for corona electrode surface removes electronics
Amount is about 4eV~5eV.Electrode may be made up of nickel, copper, silver, ferrum, steel, tungsten, carbon or platinum.The present invention is to electrode material
Type does not make specific restriction, and any material can form negative corona, about all can be made in the electronics of 4eV~5eV with producing energy
With.Therefore energy is that can be attached to kinetic energy relatively low for the electric discharge electronics of 4eV~5eV(It is about 3/2kT or 0.038eV when 25 DEG C)Low speed
Electronegative gas molecule, shifts energy, thus forming the high speed anion having compared with kinetic energy.Further, since electronegative gas
Additional charge is existed on ion, thus the potential energy of anion be possible to can be higher.Total interior energy of anion is likely to be greater than originally
Total interior energy of molecule, thus lead to H2O anion and CO2There is strong collision, produce enough energy and be used for H2O-And CO2Between
Reaction, thus shape organic molecule, such as ethanol.
The present invention does not do specific restriction to the type of device.Even so, it is believed that gas-phase reaction system uses negative electricity
Property gas, produces electronegative gas ion by electron attachment negative corona.Formed when extra electron is attached on gas molecule
During negatively charged group, due to producing corona discharge, thus it is the formation of energy 4eV~5eV's on the electronics of attachment
Powered anion and charged group.The higher electronegative gas ion of these energy electric neutrality gas molecule relatively low with energy
(As CO2)React, form organic compound(As ethanol), so that its energy reaches minimum.
If failing to form electronegativity ion by using gas, the molecule that the electronics of speed can only be larger with quality
Collide, thus the energy by electronics(As 4eV~5eV)It is transferred to gas molecule.For forming cation and electronics,
These energy may be than the ionization energy of this nonpolar molecule(As 12.6eV(CH4))Much less, therefore lack enough energy
Carry out activated atmos environment(Atmospheric temperature and pressure)Lower required reforming reaction(With CO2React).Therefore, because it is nonpolar
Molecule does not carry electronegativity gas ion, so anion cannot be formed, energy also cannot be efficiently transferred to all molecules, thus
Reduce the probability of activating reaction thing, lead in atmospheric environment(Atmospheric temperature and pressure)Under cannot complete target response.
Therefore, advantages below is had using the method for electronegative gas ion:The energy of electronegative gas ionic absorption comes
From negative corona electronics, and whole process is in relatively low temperature, pressure environment, so it is possible to avoid high using high temperature
Method under the conditions of pressure, saves consequent expense, also reduces difficulty simultaneously.Additionally, with regard to following correlative technology field
Description from the point of view of, the electronegative gas ion method that the present invention adopts and other advantages of having of equipment are also apparent
's.
Content of the invention
One aspect of the present invention is provided for synthesizing alcohol or from CO2The method extracting other organic compound;By a kind of or
Multiple electronegative gases(As vapor, ammonia, bromine, iodine and carbon dioxide)Be exposed in electron source, with formed electronegative gas from
Son.Electron source can be a kind of typical plasma source, can produce cation and anion.In an instantiation, negative electricity
Swoon for producing electronegativity gas ion source.In this case, one or more electronegative gas is exposed to negative corona discharge ring
Under border, electron attachment on gas molecule, to form electronegative gas ion.The electronegative gas ion being attached on electronics is inhaled
Receive the energy from electronics, therefore there is higher energy.Usually, the energy that electronegative gas ion absorbs from electronics
Between 4eV~5eV.The higher electronegative gas ion of energy and CO2React, generate organic compound, such as ethanol, first
Alcohol, carbamide, oxalic acid and four iodomethane.The organic compound of synthesis can be used as fuel or the industry of preparation other chemicals is former
Material.
On the other hand, method described herein is implemented using reaction vessel.Reaction vessel includes shell, shell contains attached
The multiple electrodes in container both sides.High voltage power supply provides a negative charge for electrode.Each electrode generates a negative corona, carries
For can adhere to the extra electron on electronegative gas.Using multiple air inlets by CO2It is filled with container with electronegative gas, adopt
Bubbing is removed reaction vessel by air vent.As needed, container can comprise one or more Magnet, to attract electronegativity gas
Body ion simultaneously produces the region of electronegative gas ion high concentration.
This method and equipment utilization electronegative gas ion and CO2Induction reaction, makes CO2Reduction, final synthesis of organic closes
Thing.Under normal pressure, any catalyst need not be used, make electronegative gas ion and the CO such as vapor, iodine gas, bromine gas or ammonia2Send out
Raw reaction, you can synthesizing alcohol, methanol, oxalic acid, four iodomethane, carbamide or other compounds.
Other targets of the present invention and advantage will be described in detail in specific embodiments later.
Brief description
Fig. 1 is for generating electronegative gas ion and from CO2The embodiment of the reaction vessel of anthropogenicses
Schematic diagram.
Fig. 2 shows from CO2And H2The flow chart that O manufactures the embodiment of facility of ethanol.
Specific embodiments
The attachment that with term " electronegative gas " claim employed in refer to by extra electron is described herein, it is former
Son and molecule can form the gas of anion.The implication of this paper other technologies and scientific terminology all with operation similar techniques, have
The common understanding of general technology sophistication is identical.
In the embodiment of the inventive method, the reaction vessel being adopted includes at least one and can form plasma or negative
The electrode of corona.Plasma or negative corona must have sufficiently high energy to provide electronics, thus by CO2It is converted into required
Organic product.Described below is the present invention adopts electrode to provide an embodiment of negative corona.It should be noted that this
Bright be not limited thereto, if electrode can occur the plasma discharge of routine under sufficiently high energy state, and generate
Electronics, then this electrode can also be used for the present invention.
By one or more admission line, by electronegative gas and CO2It is filled with reaction vessel.Have in synthesis such as ethanol etc.
During machine compound, can be using vapor as electronegative gas.It is filled with iodine gas, bromine gas, ammonia and CO into reaction vessel2Can close
Become other organic compound.Can be using batch or continuous operation mode, although continuous operation mode is more suitable for large number of product
Thing building-up process.
Put into multiple electrodes to produce the negative corona electric field of electrode surrounding in reaction vessel.In certain embodiments,
Electrode is linear or needle-shaped elements, has a cusp in eletrode tip.Most advanced and sophisticated can be the most advanced and sophisticated high negative charge region offer rail of next-door neighbour
Mark.The electrode being made up of nickel, copper, silver, ferrum, steel, tungsten, carbon or platinum or nickel coating electrode can be used.The present invention is not limited to certain kinds
The electrode material of type, any forms negative corona thus the material generating the electronics of energy about 4eV~5eV all can use.
Using high voltage power supply to the electrifying electrodes in container, then the most advanced and sophisticated place of electrode can form negative corona.Eletrode tip
The electronics that energy is 4eV~5eV can be generated in corona.Electronegative gas molecule near electrode(As vapor)The electricity of upper attachment
Son can generate high energy gas ion.High energy gas ion and other gas molecules mutually collide in a reservoir and have an effect, from
And synthesize various products what follows.
Generally under normal pressure or the slightly above air pressure of normal pressure, reaction vessel is operated.Reaction vessel planted agent keeps being suitable for
Temperature needed for electronegative gas and product reduction.In general, the temperature of container should be between room temperature and 100 DEG C.For example,
When using vapor as electronegative gas, for avoiding vapor in container to send out in the inwall of reaction vessel or elsewhere
Raw condensation, the temperature in reaction vessel should be up to 100 DEG C.Any one mode following can be adopted:Temperature in container is kept
The condensation of vapor below 100 DEG C, is prevented by heating chamber wall;Or inject excessive vapor into container, to protect
Hold the gaseous state vapor of abundance.When the product generating is ethanol, the temperature of container need to be maintained at 75 DEG C about, for close to boiling
The ethanol of point, temperature should be maintained at 78 DEG C about.
Reaction vessel should include the Magnet being arranged in container, to attract electronegative gas ion and to form gas ion more
For intensive region.The probability of gas ion and the mutually collision of other gas molecules so can be increased, thus initiation reaction.Work as life
Become to have higher-energy and stronger reducing power electronegative gas ion when, these gas ions can be occurred also with carbon dioxide
Former reaction, generates the organic product as needed for ethanol etc..
Although the present invention is not limited to specific reaction mechanism, inventors still think, electronics and gas ion are in corona
In be attached to each other, produce energy, so that electronegative gas ion and carbon dioxide is reacted.As long as obtaining from negative corona electron attachment
The gas ion gross energy obtaining is more than the Gibbs free energy difference of given gas reaction it becomes possible to promote reduction process further,
Obtain required organic product.For example, by following reaction(4)During generating ethanol, need three moles of vapor
Ion.Each vapor ion obtains about 5eV or 482.5 kj/mol of energy from the electronics of attachment, and then promotes anti-
Answer process.In the course of reaction forming ethanol, three moles of vapor ion can provide 1447.35 kj/mol of energy,
This is higher than the energy of required available 1306.1 kilojoules of Gibbs free energy of reaction.
Description below under corona discharge conditions by the various ions electronically forming, and in reaction vessel gas ion with
The interaction of neutral gas molecule is set forth.Under corona discharge conditions, carbon dioxide and electronics are it may happen that two kinds
The interaction of type.
co2+e-→CO+1/2O2+e-(1)
CO2Anion can be reacted with neutral gas molecule what follows, thus forming organic compound.
Although water vapour molecule does not have electron affinity because its electronic shell is closed, under corona discharge conditions,
Vapor has powerful captivation polarization to extra electron, in conjunction with extra electron, and can release energy.It is contemplated that
Under the conditions of negative corona discharge, vapor can obtain extra electron, forms H2O-.
According to process of the present invention, in normal pressure, when 50 DEG C~150 DEG C, using water vapour and CO2Gas is to generate ethanol.Institute
Containing a small amount of methanol in the ethanol being formed, perhaps also Microamounts of Oxalic Acid as by-product.It is likely to form dioxy as above
Change carbon ion.Under corona discharge conditions, the forming process of vapor ion is as follows:
HzO+e-→H2O-(3)
Water vapour ion and carbonic anhydride ion can be reacted with neutral gas molecule in the reactor, form ethanol.
It is believed that CO2The reaction mechanism being converted into ethanol is as follows:
3H2O-+2CO→C2H5OH+202+3e-(4)
3H2O-+2CO2→C2H5OH+3O2+3e-(5)
Methanol forming process in the reactor is as follows:
4H2O-+ZCO2→2CH3OH+3O2+4e-(7)
2H2O-+CO→CH3OH+O2+2e-(8)
Oxalic acid forming process in the reactor is as follows:
Ammonia is a kind of electronegative gas, can adhere to electronics by following reactive absorption under corona discharge conditions:
Ammonium ion can occur following reaction with carbon dioxide or carbon monoxide in the reactor, forms carbamide:
Iodine is also a kind of electronegative gas, can form anion under corona discharge conditions, when temperature is 70 DEG C, can be two
Four iodomethane are successfully synthesized, conversion ratio is up to 88%, and step is as follows in carbonoxide:
According to the difference of required product, when carrying out method provided by the present invention, it would however also be possible to employ other electricity
Negativity gas, such as chlorine or bromine.
There is enough energy by CO2Other electronics source being converted into organic productss is it can also be used to the inventive method.Electricity is negative
Property gas ion also can by other non-thermal or heat plasma technology or anion ion source produce, including altofrequency method,
Such as radio frequency plasma(RF), microwave plasma, inductively coupled plasma(ICP), and high voltage method, such as electricity
Dielectric barrier discharge(DBD)And electron beam(EB).Any generation has enough energy and CO2The electronegative gas reacting
The method of ion, is used equally to 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, shell can be steel, rustless steel or any other applicable material.Because reaction is at atmosheric pressure or closely air
Carry out under pressure, so the thickness of shell can as little as 1/4 inch.
Lining 117 can be built in shell, reduce the probability that shell of reactor occurs electric shock.Lining 117 can for nickel or
Other applicable materials.If necessary, insulant can be added between inside and outside shell, or inner shell be carried out add using appropriate device
Heat, reduces water vapour or product condenses, and heater can be steam jacket heating.
Multiple electrodes 116 are connected with the inwall of reactor.Electrode can be for carrying cuspidated needle-like or wire electrode;Electrode material
Matter can be nickel, copper, silver, ferrum, steel, tungsten, carbon or platinum, or any can be used for electrode, producing negative corona near electrode thus generating
There are other applicable materials of the electronics of about 4eV~5eV energy;Electrode can coat metallic catalyst, available precious metal catalyst
Agent has:Nickel, rhodium, cobalt, phosphorus, caesium and platinum.Any noble metal catalyst that can produce the electronics with about 4eV~5eV energy, all
Can use.
Negative high voltage power source(In figure does not show)It is connected with multiple electrodes 116.In an embodiment, negative high voltage power source provides at
1 kilovolt of voltage.Voltage(Intensity)Selection should meet following condition, i.e. make to be delivered to the electronegative gas of reactor anti-
Answer room 118 interior energy by height ionizing.
In operation, when electrode 116 is encouraged by negative high voltage power source, eletrode tip forms negative corona, is then formed
Negative electricity is had stage fright.Electronegative gas, such as water vapour, reactor is delivered to by air inlet 113.Water vapour enters reative cell, exposes
Have stage fright in negative electricity produced by eletrode tip.Charged electron in corona is attached to hydrone, forms electronegativity water ion.
Carbon dioxide is delivered to reactor by air inlet 113, and partial CO 2 molecule can adsorb powered in corona field
Electronics, thus form electronegative carbon dioxide molecule.Powered water vapour/carbonic anhydride ion and neutral water vapour/dioxy
Change carbon molecule to react, form ethanol.When vessel temp is maintained at more than 78 DEG C, alcohol vapour, together with byproduct of reaction,
Part water vapour and CO2Together, discharged by air vent 110.If product is liquid form, can in reactor bottom plus
One exhaustor, for collecting reaction product.
In an embodiment, cylinder 112 is used in the reactor containing bar magnet or magnetic bead.Cylinder 112 can be made up of wire netting, such as nickel
Net, nickel sponge, platinum guaze or Graphene, so that the bar magnet of absorption the inside or magnetic bead.Bar magnet or magnetic bead produce magnetic around cylinder 112
, attract electronegative water vapour ion and carbonic anhydride ion, thus forming dense gas ions, cylinder 112 can be by holding
Support tube 115 in device supports.The flow chart of exemplary ethanol production facilities is shown in Fig. 2, and steam generator 210 enters by first
QI KOU 214, water vapour is delivered to reactor 212.Carbon dioxide source 216 passes through the second air inlet 218, and carbon dioxide is conveyed
To reactor 212.When liquid or solid carbon dioxide source of the gas are used as source of the gas, should be using control conversion equipment.
Water vapour is ionized in the reactor, simultaneously with CO2React, form ethanol as above.Ethanol produces
Thing, with the by-product such as water vapour and methanol, oxalic acid, is discharged reactor by air vent 220, is then sent to condenser 222
In, it is condensed into liquid, then is transported to distilling apparatus 224 from condenser 222, carry out the isolation and purification of ethanol.From distilling apparatus
Product out, its ethanol content may be up to 95%.
If necessary, from distilling apparatus, product out can be delivered to ultrafiltration apparatus 226, forms final second
Alcohol product.
In view of those of ordinary skill in the art will readily appreciate that methods described herein, thus the above embodiment of the present invention and its
Its embodiment all changes and changes, but can not exceed the restriction scope of claims.It is therefore preferable that embodiment is detailed
Description should be illustrative, and non-limiting.
List of references
The all publications and patents being mentioned herein, including project set forth below, are all hereby incorporated by reference, such as in full
With each single publication or patent application by especially be individually hereby incorporated by reference the same.If any conflict, with
Present patent application(It is defined including herein)It is defined.
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Claims (12)
1. a kind of is the method for organic compound by carbon dioxide conversion, the method comprising the steps of:
At least one electronegative gas of mixing and titanium dioxide in there is at least one container for the electrode that forms negative corona
Carbon;
Negative voltage is applied at least one electrode described, thus to produce negative corona discharge in the most advanced and sophisticated of described electrode, thus raw
Become electronegativity ion, the energy of described electronegativity ion be enough to described carbon dioxide conversion be organic compound, wherein negative electricity
Corona produces electronics, and
Described conversion process is carried out in negative electricity is had stage fright,
Wherein, when described electronegative gas is vapor, described organic compound is ethanol;When described electronegative gas is ammonia
During gas, described organic compound is carbamide;Or when described electronegative gas is iodine gas, described organic compound is tetraiodo first
Alkane.
2. a kind of by carbon dioxide conversion for organic compound equipment, described equipment comprises:
Inner shell, described inner shell is defined to reaction vessel in shell;
At least one electrode being connected with negative high voltage power source, described electrode is connected with the inwall of described reaction vessel, and described electricity
The tip of pole is located in described reaction vessel;
It is added with insulant between described shell and inner shell;
At least one air supply pipe, described air supply pipe provides electronegative gas and carbon dioxide to described reaction vessel;And
Outlet tube, product is removed described reaction vessel by described outlet tube,
Wherein, described reaction vessel is operated in negative electricity is had stage fright, and
When described electronegative gas is vapor, described organic compound is ethanol;When described electronegative gas is ammonia,
Described organic compound is carbamide;Or when described electronegative gas is iodine gas, described organic compound is four iodomethane.
3. equipment according to claim 2, wherein, described electrode is the shape of pin or line.
4. equipment according to claim 3, wherein, described electrode is made up of metal, described metal be selected from nickel, copper, silver,
Ferrum, the group of steel, tungsten or platinum composition.
5. equipment according to claim 3, wherein, described electrode is made up of carbon.
6. equipment according to claim 4, wherein, described electrode is coated with catalyst, described catalyst be selected from nickel,
The group that rhodium, cobalt, phosphorus, caesium and platinum are constituted.
7. equipment according to claim 4, described equipment is also included in the unit in induction magnetic field in described reaction vessel.
8. equipment according to claim 4, described equipment also comprises the metal cylinder being fixed in described reaction vessel, its
In, described metal cylinder comprises multiple bar magnets or magnetic bead.
9. equipment according to claim 8, wherein, described metal cylinder is wire netting.
10. equipment according to claim 9, described wire netting be selected from nickel screen, be coated with catalyst copper mesh, sponge nickel
The group that the nickel screen of the nickel screen of parcel and graphite parcel is constituted.
11. a kind of carbon dioxide conversion is the method for organic compound, the method comprising the steps of:
Mix at least one electronegative gas and carbon dioxide in the container have at least one electron source, described electron source is used
In formation anion;And
In the above-described container electron discharge, thus generating electronegativity ion, described electronegativity ion are produced by described electron source
It is organic compound that energy be enough to described carbon dioxide conversion,
Described conversion process is carried out in negative electricity is had stage fright,
Wherein, when described electronegative gas is vapor, described organic compound is ethanol;When described electronegative gas is ammonia
During gas, described organic compound is carbamide;Or when described electronegative gas is iodine gas, described organic compound is tetraiodo first
Alkane.
12. methods according to claim 11, wherein, described electron source is selected from radio frequency plasma (RF), microwave etc.
The group that gas ions, inductively coupled plasma (ICP), electrolyte obstacle electric discharge (DBD) and electron beam (EB) are constituted.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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US201161575264P | 2011-08-19 | 2011-08-19 | |
US61/575,264 | 2011-08-19 | ||
CN2011102682834A CN102993053A (en) | 2011-09-28 | 2011-09-28 | Electronegative plasma assisted carbon dioxide emission reduction processing method and device thereof |
CN2011102682834 | 2011-09-28 | ||
CN201110268283.4 | 2011-09-28 | ||
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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CN103796751B true CN103796751B (en) | 2017-02-15 |
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CN111186816B (en) * | 2020-01-17 | 2022-04-01 | 西安交通大学 | Plasma carbon sequestration system and method |
CN112113497B (en) * | 2020-08-17 | 2021-12-21 | 华南理工大学 | Self-healing resistance type strain sensor and preparation method and application thereof |
CN114307908B (en) * | 2022-01-19 | 2023-03-28 | 华中科技大学 | Method for synthesizing C8+ aviation fuel oil by catalytic hydrogenation of carbon dioxide |
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US4572759A (en) * | 1984-12-26 | 1986-02-25 | Benzing Technology, Inc. | Troide plasma reactor with magnetic enhancement |
DE3776187D1 (en) * | 1986-04-17 | 1992-03-05 | Eltech Systems Corp | ELECTRODE WITH PLATINUM METAL CATALYST IN THE SURFACE LAYER AND THEIR USE. |
JPH0576723A (en) * | 1991-09-25 | 1993-03-30 | Kumagai Gumi Co Ltd | Method for reducing greenhouse-effect gas |
RU2234457C2 (en) * | 2001-06-01 | 2004-08-20 | Общество с ограниченной ответственностью "Научно-производственная компания "НеоТекПродакт" | Method of production of fulleren-containing carbon black and a device for its realization |
TWI424980B (en) * | 2008-02-04 | 2014-02-01 | Nat Univ Tsing Hua | Carbon dioxide converts to useful organic products by using plasma technology |
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2012
- 2012-08-17 AR ARP120103043 patent/AR087595A1/en unknown
- 2012-08-17 CN CN201280040307.3A patent/CN103796751B/en not_active Expired - Fee Related
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