CN101357750A - Method and device of microwave excitation molten salt catalytic reforming gasification carbon group compound - Google Patents
Method and device of microwave excitation molten salt catalytic reforming gasification carbon group compound Download PDFInfo
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Abstract
The invention belongs to the technical field of preparing clean fuel gas and chemical engineering synthesis gas, concretely, a method and equipment for reforming and gasifying carbon-based compounds through microwave excitation molten salt. The invention is characterized in that the reactor wall is manufactured by pottery material oxygenated by heat resistance and microwave inertia to recycle water vapor produced by the afterheat to replace air (or pure oxygen) as gas agents and oxygen source. Microwave is continuously irradiated from the outside to the reactor; electromagnetic energy is transformed into heat energy by microwave-induced fever bed material (also as catalyst); meanwhile, electrodeless discharge reaction is triggered. Under a flow craft, the reforming and gasifying processing to the carbon-based compounds is completed by the electrodeless discharging reaction motivated by microwave, thus obtaining reforming gas with H2, CO and CO2 as the main body. The purpose of the invention lies in solving various problems which are difficult to be overcome with various former techniques by using a simple, fast and high efficient method.
Description
Technical field: the technical field that the invention belongs to preparation clean gas and chemical industry synthetic gas.Specifically, be the method and apparatus of carbon group compound being reformed and being gasified by microwave excitation molten salt.
Background technology: microwave has very strong penetrativity, i.e. " internal heating " effect.Can see through wall of container optionally, the material of the absorbed microwave energy in the heating container equably, avoid the loss of energy in conductive process.Microwave heating technique has obtained application in fields such as metallurgical and ceramic post sinterings.Present technique has been used for reference these successful experience, and various carbon group compounds apply transformations to gasify.
Gasification technology occurs counting from " gasification " speech in 1790, researches and develops more than 200 year, and technology and control become increasingly complex, and unsurmountable defective is still arranged.The design of tradition vapourizing furnace is the heat energy that adopts " partial oxidation burning " process to discharge, to keep the required endothermic process of pyrolysis gasification.But because combustion processes is swift in response, solid fuel is transformed into the volume rapid expansion behind the gas, and temperature can not be concentrated, and the energy relative deficiency of thermopositive reaction is to keep the required of thermo-negative reaction, cause the endothermic pyrolysis reaction to carry out not exclusively thus, show as and produce a large amount of oil smoke.If the tradition gasification mode as vaporized chemical, can be brought nitrogen with air into, make nitrogen proportion increasing in the product gas, hinder follow-up chemical utilization.If as vaporized chemical, can increase the power consumption of air separation with pure oxygen, system's structure and complicated operation are monopolized by foreign technology substantially.
The high pressure of supercritical steam reformation gasifying reactor (25～30MPa) and the strong well-oxygenated environment of high temperature (650 ℃), have to use expensive corrosion-resistant and high voltage bearing alloy material to make container.Even so, the corrosion phenomenon of material still makes us startling.Oxidation corrosion and high pressure are the potential risks of its safe operation.
Summary of the invention:
Goal of the invention: the invention provides a kind of method and apparatus of microwave excitation molten salt catalytic reforming gasification carbon group compound, its purpose is to solve the variety of issue that various technology in the past are difficult to overcome with a kind of simple and direct, high-efficiency method.
Technical scheme:
A kind of method of microwave excitation molten salt catalytic reforming gasification carbon group compound, it is characterized in that: with the ceramic material reactor wall of microwave inertia and heat-resisting oxidation, expect the double as catalyzer with fused carbonate as the heating bed, be transported in the reactor as material to be machined with carbon group compound, be passed in the reactor as vaporized chemical with water vapor, from the outside continuously to reactor internal irradiation microwave; Fused carbonate in the reactor is converted into heat energy with electromagnetic energy, and causes the electrodeless discharge reaction, reacts the reformation gasification process of finishing carbon group compound by electrodeless discharge, obtains with H
2With CO, CO
2Reformed gas for main body.
Described fused carbonate is one or more in yellow soda ash, salt of wormwood, the Quilonum Retard, and comprises their precursor, such as above-mentioned three kinds of alkali-metal oxyhydroxide, formate, supercarbonate; Comprise that also above-mentioned three kinds of alkali-metal fused carbonates decompose sodium oxide, potassium oxide, the Lithium Oxide 98min that the back forms.
Described carbon group compound is meant the material that contains carbon in material molecule is formed, and comprises the mixture of hydrocarbon polymer, carbohydrate, simple substance carbon material and various carbon and oxygen, sulphur compound.
Described water vapor and other vaporized chemical are united reformation, other vaporized chemical be purity oxygen, carbonic acid gas or airborne one or more, the oxygen level of being brought into by water vapor accounts for more than 50% of the total oxygen-supplying amount of various vaporized chemicals, mixes the oxygen level that other vaporized chemical of using brings into it and accounts for 0～50%.
The range of frequency of described microwave is between 300MHz to 300GHz, and the temperature in the power 〉=5W, reactor is controlled at 650～1100 ℃, and pressure range is at 0.1～1MPa.
A kind of equipment of aforesaid microwave excitation molten salt catalytic reforming gasification carbon group compound, it is characterized in that: in a metal shell, be provided with a reactor with the ceramic material of microwave inertia and heat-resisting oxidation, be connected to the pipeline that feeds a plurality of water vapors or other vaporized chemical in the reactor, a feeding screw also is connected in the bottom of reactor, bottom at reactor also is provided with slag-drip opening, and the top of reactor is communicated with the outlet of reformed gas; Being provided with the microwave energy-feeding mouth on metal shell is arranged on and the corresponding position of reactor.
The microwave energy-feeding mouth adopts x axle, y axle, z axle three-dimensional space layout or two-dimensional space layout with respect to the reactor of cylindricality.
The reactor wall of the ceramic material of microwave inertia and heat-resisting oxidation, the stupalith of employing are aluminium sesquioxide pottery, aluminum silicate ceramic, magnesia ceramics.
Reactor wall is provided with lagging material outward, mushy structure that material adopts materials such as aluminium sesquioxide pottery, aluminum silicate ceramic, magnesia ceramics, silicon-dioxide to make.
Metal shell is provided with Cryogenic air import and high temperature air outlet, forces the air cooling circulation.
Advantage and effect:
1, fused carbonate is that good microwave causes heating element and heat and mass.Can rely on and processed the most comprehensive contact of material, will be heat passage to the latter.
2, fused carbonate is good reforming reaction catalyzer, and cheap and easy to get, easy recovery.
Because microwave heating has selective excitation, the specific inductivity of catalyzer (fused salt and charcoal) is big, is " focus " and " active center " of electrochemical reaction that electromagnetic energy transforms.Solid-state or liquid carbon based compound is broken down into gasiform lower carbon number hydrocarbons or tar gas at the interface catalyzer/reaction substrate.The latter's thoroughly cracking of quilt in microwave plasma again.Adopting at high temperature is that the obvious benefit of liquid catalyst is, be not subjected to solid catalyst physical strength, thermo-chemical stability, reusability, with the restriction of the factors such as surperficial contact of reactant.
3, fused carbonate technology can be system gas and desulfurization, remove white residue and combine, product gas impurity is few, calorific value is high, can be directly used in downstream production, has simplified cleaning section.This point is to high sulfur-bearing raw material, and is especially favourable as the processing of junked tire and coal etc.
4, technological operation complexity is low, controllability is good.Can unite reformation with various vaporized chemicals, the accounting of hydrogen in the reformed gas is adjusted flexibly according to the requirement of raw material and downstream process.Simultaneously can with CO
2The capture technique combination reduces greenhouse gas emission.
The electric heating conversion efficiency of microwave (80～95%) is higher than the hertzian wave of other frequency range.Layout energy field neatly adopts high temperature electrodeless discharge pattern can finish the puzzlement that thermoelectrochemistry transformed and avoided electrode problems efficiently in addition, has other technology incomparable advantage.
5, processed raw material is suitable for face width, can utilizes low grade coal and various waste resource, even the discharging that can be applicable to administer organic waste.
Description of drawings: Fig. 1 is the primary structure synoptic diagram of present device.
Embodiment:
The present invention is with the ceramic material reactor wall of microwave inertia and heat-resisting oxidation, and the water vapor that produces with recovery waste heat replaces air (or pure oxygen) as vaporized chemical and oxygen source., cause heating bed material (catalyzer of holding concurrently) by microwave electromagnetic energy is converted into heat energy, and cause the electrodeless discharge reaction continuously to reactor internal irradiation microwave from the outside.Under flow process, in time, react the reformation gasification process of finishing carbon group compound by the electrodeless discharge under the microwave excitation in the several seconds.At reactor lower part, solid-state or liquid carbon group compound and fused carbonate are at first become gasiform lower carbon number hydrocarbons or tar gas by catalytic pyrolysis in solid-mode that melt directly contacts.In the microwave discharge plasma of reactor top charring layer, lower carbon number hydrocarbons or tar gas are again by cracking and reformation up hill and dale.Obtain with H
2With CO, CO
2Reformed gas for main body.Technological design combines compression process, cleaner production system reformed gas and desulfurization, except that white residue.
How at first illustrate present technique works.
With fusion yellow soda ash (Na
2CO
3) cause heating bed material as microwave,, as processed raw material the gasification reaction temperature is set in more than 850 ℃ with coal or stalk, pressure is greater than 0.1MPa, microwave frequency 2.45GHz.
Talk about from sodium hydroxide (NaOH) earlier.Because it is the transition compound in this reaction system, also can be the precursor of fusion yellow soda ash.
The fusing point of NaOH is 318.4 ℃, than being easier to be heated fusing.The same with many ionic compounds, NaOH is not obvious to microwave absorbing in low-temperature zone.This is not serious, mixes 5～15% powdered carbon therein and causes heating element as the low-temperature zone microwave, and powdered carbon can help intensification and the fusing of NaOH.Fused NaOH is that good microwave causes heating element.The commitment that heats up has a spot of cigarette and occurs.Cigarette is the aerosol shape of tar when high temperature, and the cooling after coagulation becomes tar.What tar produced when 500 ℃ of left and right sides is maximum.But after reaching the temperature of setting, tar is just cleaved.The charcoal that consumes in the reaction can constantly obtain replenishing of coal or stalk charcoal.So, in whole reaction system and have no lack of microwave and cause the heating medium.
In low-temperature zone, NaOH can with the CO reaction that generates in coal or the gasifying stalk process, form sodium formiate (HCOONa, 253 ℃ of fusing points).The fusion sodium formiate is very unstable, along with the rising of temperature is broken down into CO, water vapor and sodium oxide (Na
2O, 920 ℃ of fusing points, the temperature of distillation is at 1275 ℃).NaOH after the fusing also is broken down into water vapor and Na gradually
2O.Water vapor has then been participated in the reformation gasification reaction of coal or stalk directly.
Na
2O also can with the CO that generates in coal or the gasifying stalk process
2Reaction forms yellow soda ash (Na
2CO
3, 851 ℃ of fusing points).Na
2CO
3More stable, just begin a small amount of decomposition when surpassing fusing point, resolve into CO
2And Na
2O.So, reach the temperature of setting after, Na
2CO
3And Na
2O is the advantage melt, with Na
2CO
3Be main.
NaHCO
3Change into Na at 270 ℃
2CO
3, H
2O and CO
2, other in like manner.
Be example with the sodium salt above, the conversion of potassium and lithium salts in like manner.
Fused carbonate is that good microwave causes heating element.Still good heat and mass can be used as " heating bath medium " and comes carbon group compounds such as " immersion, boiling, melting " stalk or coal.
In addition, Na
2CO
3And Na
2O can also double as be the catalyzer of pyrolytic reaction.They were used more than 100 year by people so far as the pyrolysis catalytic agent.
Fused carbonate is also as environment harmful element scavenging agent.Such as, with element sulphur reacting generating salt slag in the raw material and it is disposed, make and do not contain hydrogen sulfide (H in the reformed gas
2S) gaseous constituent.All contain H in the product gas of other gasification technology
2S gas needs first desulfurizing and purifying during as synthetic gas.
Besides do not participate in the outlet of the element that reacts under bright technology.
The principal element that does not participate in coal or the stalk reacting is silicon, sulphur, nitrogen etc., and potassium will participate in alkali-metal recycling.
Silicon is the element of the maximum deal that do not participate in reacting.Silicon can form water glass in fused carbonate gasification reaction system.The relative density of water glass is 2.614g/cm
3Pay close attention to relative density and be in order to determine that it is positioned at the top of reactor, middle part, or bottom, relates to the position of deslagging.
Sulphur changes into sodium sulfate (Na in fused carbonate gasification reaction system
2SO
4, relative density 2.68g/cm
3, 884 ℃ of fusing points).
The outlet of nitrogen is mainly in product gas.
Na
2The relative density 2.27g/cm of O
3, Na
2CO
3Relative density 2.53g/cm
3Both relative densities are all less than water glass and sodium sulfate.Deslagging can carry out in the bottom of reactor.
Form corresponding calcium salt if in whole gasification reaction system, exist a spot of calcium constituent can have precedence over water glass, sodium sulfate, yellow soda ash.The relative density of calcium salt is at 2.7～3.2g/cm
3Between, at the bottom of reactor deslagging.The reaction of magnesium and calcium is similar.Aluminium and ferro element form the oxide compound sediment.Phosphorus is deposited discharge with the pyrophosphate salt form.
In this technology in the consumption of NaOH and the raw material content of impurity such as silicon, sulphur be directly proportional.
To the slag of discharging, carry out the treating processes that alkali reclaims, be similar to the last handling process of caustic soda legal system paper pulp from the melts of alkali recovery furnace discharge.
Also can use single anode membrane electrodialysis to reclaim the method for alkali.Like this, both reclaim basic metal, isolated impurity such as sulfuric acid, silicic acid again, avoided discharge of poisonous waste.
The carbonate that uses in this technology comprises following alkali-metal carbonate: sodium, potassium, lithium.
618 ℃ of Quilonum Retard fusing points, 735 ℃ of boiling points; 891 ℃ of salt of wormwood fusing points; Potassium oxide (K
2O) fusing point is 881 ℃, 1350 ℃ of sublimation temperatures.
Feed intake except can directly using the carbonate of above-mentioned metal as catalyzer.Because the precursor of these metal carbonates can change into the carbonate of respective metal in reactor, so, feed intake as catalyzer and can also use following compound: the supercarbonate of the oxyhydroxide of above-mentioned metal, the formate of above-mentioned metal, above-mentioned metal.
Potassium oxide and sodium oxide can be operated in the temperature more than 900 ℃.Because they are the products after the carbonate decomposition, so the carbonate of present technique indication also comprises this two kinds of compounds.
The fusing point of comprehensive sodium, potassium, lithium carbonate, their fusing point and the sublimation temperature of oxide compound, the optimal temperature scope of implementing present technique is 650～1100 ℃.
The suitable pressure range of present technique is 0.1～1MPa.
The mixture that can be comprised hydrocarbon polymer, carbohydrate, simple substance carbon material and various carbon and oxygen, sulphur compound by the various carbon group compounds that present technique is processed is as coal, various biomass (various stalks and forest industry waste etc.), oil and derivative thereof, rubber, plastics, synthetic or natural fiber, municipal solid wastes (MSW), paper and black liquid, xylogen, tar, pitch, charcoal, coke, carbon black etc.
Description to working condition in the reactor:
Operating mode in this process reactor is similar to the operating mode in " electrode salt bath furnace ", and what this technology that different is was used is high frequency alternating electric field and electrodeless discharge.
The inlet of material and water vapor should be opened the bottom at the column reforming reactor.Owing to the reason reaction material of proportion can spontaneously move to top.The various tar components of not degraded by the degree of depth " are clung " in the meeting of high viscous fused carbonate melt.The column reforming reactor can increase tar gas residence time at high temperature.Tar is come from water vapor " active oxygen " and has been decomposed when being stuck, when steam is not enough just by charing.Tiny carbon granule disperse forms slurry (slurry) in fused salt, (direct carbon fuel cell, operating mode DCFC) is identical with direct carbon conversion fuel cell for its operating mode.The carbide that is agglomerated into bulk can cover the upper strata of fused salt slurry naturally, and formation can absorb the charing bed bed of material of microwave power.If there is not the cooling effect of bottom ascending gas, the carbide layer can rise quickly to more than 1000 ℃ from room temperature under microwave radiation in a short period of time, and plasma discharge takes place, and its operating mode is enough to decompose the tar gas in the lower floor.Lower carbon number hydrocarbons and tar gas that lower floor's reaction generates can filter, adsorb and decompose in this zone.The principal element that influences this regional volume size is the input of water vapor.Water vapor be oxygen source also be hydrogen source, the both is the charcoal reagent that disappears.And the water vapor amount is easy to control.Reported by many scholars with the research of carbide catalytic tar cracked.By microwave excited charcoal, but the better catalytic effect of mat plasma discharge reaction performance.Under the excessive condition of water vapor, the carbide layer can disappear.At this moment, in the process of product gas heat exchange cooling outside reactor, water-gas shift reaction taking place, makes H in the product gas
2And CO
2Proportion increases, and CO proportion reduces.So the water vapor input is the important means of regulating each component proportion in the product gas.The required water vapor amount of decomposing biomass obviously is less than the required water vapor amount of coal of decomposing.In view of this, the product gas through behind this three phase boundary (solid, liquid, gas/plasma body) the fused salt slurry bubbling column reforming reactor can reach the effect of an one way with regard to the Ex-all tar ingredients.
Existing discovering, semiconductor material are the cartridges of microwave radiation, i.e. " microwave causes heating element ".
Having preferably, the specific conductivity of the semiconductor material of microwave absorbing property (σ) is generally 10
-3Scm
-1～10
0Scm
-1
Above-mentioned parameter is the data under the normal temperature condition, lists the conductivity data of associated materials under condition of different temperatures below.
NaOH is 2.38Scm in the electric conductivity of 350 ℃ (fusions)
-1
Na
2CO
3Electric conductivity 850 ℃ (fusions) is 2.37Scm
-1
Simple glass under the molten state (contains Na
2O) specific conductivity is 10
-1～10
0Scm
-1
Graphite is 332Scm 25 ℃ specific conductivity
-1
Charcoal is 10 25 ℃ specific conductivity
-1～10
0Scm
-1
Coal is 10 25 ℃ specific conductivity
-2～10
0Scm
-1
These data show, the NaOH under the molten state, Na
2CO
3, Na
2The conductivity data of O has all dropped between the microwave absorbing sensitive area.
Charcoal and coal have also dropped between the microwave absorbing sensitive area.But, they are not ionic compounds, inhale the ripple reaction and are subjected to influence of temperature change very little.
In this technological temperature interval, charcoal has the microwave absorbing activity between the whole district; And carbonate only has the microwave absorbing activity in the medium and high temperature interval.
Charcoal causes heating element as microwave and has obtained application in microwave-carbon heat reducing method metallurgical technology.
Fused salt is the ionogen in the microwave electric field, therefore their catalytic effect has tangible electrochemical characteristic, the energy of loss can obtain in time replenishing of electromagnetic energy, and this effect can cause the various chemical reactions that could take place when finishing relatively-high temperature under low relatively temperature.
Above-described is separately with the reformation gasification reaction of water vapor as vaporized chemical.In addition, water vapor can also with pure O
2, CO
2, vaporized chemical such as air unites the gasification of reforming.The implication of associating reformation is that the oxygen level of being brought into by water vapor accounts for more than 50% of the total oxygen-supplying amount of various vaporized chemicals.Other can be united the oxygen that the various vaporized chemicals of use bring into water vapor and account for 0～50%.
Water vapor and pure O
2The benefit of associating reformation is because reduced the required energy consumption of water decomposition, can reduce total power consumption significantly.
Water vapor and CO
2The benefit of associating reformation is to adjust H in the product gas flexibly
2The ratio of/CO, the chemical industry that is beneficial to the downstream is synthetic.
The benefit that water vapor and air are united reformation is to have reduced the required energy consumption of water decomposition, though increased a certain amount of N in the product gas
2, but little for the ammonia synthesis process influence in downstream.
Be description (see figure 1) below to microwave energy field structure beyond reactor wall, the reactor:
Usually (corresponding wavelength is 100～0.1cm) to the range of frequency of the microwave of scientific and technological circle's definition between 300MHz to 300GHz.Except different wave-sucking performance difference of expecting can influence the degree of depth of microwave penetration, the degree of depth of microwave penetration material was also relevant with wavelength and frequency.Frequency is high more, and wavelength is short more, and its penetration power is also weak more.Because it is thicker to produce the diameter of the reactor 2 that is adopted, suitable microwave frequency should be selected between 300MHz to 30GHz.Such as, 915MHz and 2.45GHz.
The height of reactor mainly needs the resident time relevant with reforming temperature and product gas, and relevant with the character and the particle diameter of reaction material.When reforming temperature is low, complete for decomposition reaction, need the resident time of product gas long, the height of reactor needs corresponding increase.
The making material require of feeding screw 4 uses above-mentioned pottery, or with the metal of above-mentioned ceramic coating.
Water vapor input aperture and valve thereof are made material require and are used above-mentioned pottery, or with the metal of above-mentioned ceramic coating.
Slag-drip opening 7 and valve thereof are made material require and are used above-mentioned pottery, or with the metal of above-mentioned ceramic coating.
Temperature probe and signal transmission path need use material and the technology that is not subjected to microwave interference.Such as fibre optic thermometer etc.But the part in reactor needs good thermo-chemical stability.
Microwave energy-feeding mouth 6 can adopt x axle, y axle, z axle three-dimensional space layout with respect to the layout of cylindricality reactor 2, also can adopt the two-dimensional space layout, or even orientation word order from top to bottom.The quantity of microwave energy-feeding mouth 6 and the output rating of each mouthful can increase and decrease in service can the switching flexibly flexibly according to the layout needs of energy field.
Mark among Fig. 1 is respectively: the outlet 5 of the pipeline 3 of metal shell 1, reactor 2, water vapor and other vaporized chemical, feeding screw 4, reformed gas, microwave energy-feeding mouth 6, slag-drip opening 7, Cryogenic air import 8 and high temperature air outlet 9.
Set forth some principles of present technique below:
The micro-wave dielectric heating comes from medium the electricity of microwave is led loss and polarization loss, leads the contribution of loss under the hot conditions based on electricity.
Fused salt absorbs behind the microwave mainly with ionic conductance loss electromagnetic energy.For fused salt, temperature raises, and the lattice resistance that viscosity degradation, ion motion are subjected to reduces, and specific conductivity is increased.During the fused salt ion migration, the energy that they are absorbed is partly passed to molecule on every side in electric field, electromagnetic energy is changed into the thermal vibration of molecule, energy expenditure makes on the dielectric medium pyrogenic effect.Its essence is the non-simple harmonic quantity scattering between the phonon.
In this technology, charcoal and coal microwave-absorbing heat-generating belong to electronic conductance loss (but the mineral substance generating unit segregant electricity that exists is led loss) in the coal of low metamorphic grade.Charcoal is made of the graphite microcrystal body.In graphite crystal, carbon atom is with sp
2Hybridized orbital has formed big π key and delocalized electron.Delocalized electron carries out communization motion in whole crystal, after charcoal absorbs hertzian wave, be converted into heat energy by delocalized electron with the form of resistance losses.The ionic conductance loss all is a joule loss with the electronic conductance loss, and both heat effect mechanism is consistent, all follows Joule-Lenz's law.
Coal is the polymerization aromatic hydroxy compound.On its structure aromatic ring conjugated similar to graphite crystal and delocalized electron are arranged also.Charcoal and coal all are because delocalized electron has been arranged, so can present the feature of electronic conductance loss in microwave electric field.
Microwave-fused salt reformation gasification reaction system is an electrolyzer reactive system that is similar to synthesis by internal resistance electric melting, and promptly electric energy changes into system chemical energy, charging.Different is, its electric field is not a DC electric field, but the alternating electric field of a high frequency.Therefore, be an electrodeless electric field.In reaction system, water and carbon group compound at fused salt and Pd/carbon catalyst at the interface or/and become H by " electrolysis " in the plasma reaction
2And CO.
In the DC electric field in the electrolysis of water and the microwave alternating electric field difference of the electrolytic reaction route map of carbon group compound as follows:
The electrolyzer reaction of water: get betatopic electrode reaction → chemical energy in electric energy → DC electric field.
Organic electrolyzer reaction: the betatopic semi-conducting electrode that gets under electric energy → microwave electric field reacts or/and the electrochemical reaction → chemical energy in the plasma body.
That is microwave fused salt semi-conducting electrode reaction is or/and the electrochemical reaction of electrode interface in the electrochemical reaction=DC electric field in the microwave plasma.
In reforming the gasification reaction system, microwave-fused salt do not have obvious isolating yin, yang electrode and circuit in DC electric field, therefore new energy matter is not that electrode surface at macro-size produces, betatopic reaction is to take place in the fused salt semi-conducting electrode at the interface (electrode of microscopic dimensions) of catalyzer/reaction substrate and plasma body.The kinetic energy that obtains in electric field in view of electronics in the plasma body (electronic induction quickens or induced electromotive force) is equal to the electromotive force of electrode reaction, the electrons/ions reaction interface of setting up in the plasma body is equal to the electrode/electrolyte reaction interface, and the electric current in the plasma body is equal to electrode current.So, plasma chemical reaction and electrode chemical reaction can be treated on an equal basis.That is, all be the reaction that electric field energy is converted into energy in the novel substance.
Reaction process is such: in magnetron, the electronics of emission of cathode is done in the retarded motion process of circling round in anode, and the high voltage direct current potential energy of electronics is converted into microwave power.With microwave power feed-in reformer, constitute the microwave absorbing load by radiation by the dielectric medium in the reformer.If there is not absorbing load, accumulative electric charge and high field can puncture the air dielectric in the cavity in microwave resonance cavity, and the microwave gas discharge promptly takes place.Fused salt and charcoal in the reformer are high dielectric loss materials, high-frequency electrical magnetic energy can be converted into loss heat.The rule of arranging according to common energy: plasma body＞gas＞liquid＞solid.Gas between fused salt catalyzer and the reaction material (vapour) crack can become the action space of plasma discharge.The thermal ionization environment has been created plasma discharge and has been generated the condition (reformer air outside medium does not possess the thermal ionization environment) of chemical reactivity species.Field emitted electron in the microwave electric field (come from the compacting of electric field to surface potential barrier, work function is reduced) and thermic emitting electrons become the " unbound electron of ignition in hydriding plasma discharge.Unbound electron obtains kinetic energy under the acceleration of microwave oscillation electric field, and with catalyzer/reaction substrate gas at the interface in various heavy particles (all quality are greater than the particle of electronics, as ion, atom and molecule etc.) generating collision, cause the reaction of avalanche ionization and plasma discharge.When high-energy electron and various heavy particle generation radiative collision, make heavy particle be excited (the electronic orbit transition makes heavy particle be transformed into high-energy state from low-energy state), dissociate (after the covalent linkage homolysis generate two free radical particles), ionization (generating positive and negative ion or radical ion), the kinetic energy of electronics is converted into the static potential energy of active particle.The ion of these high potentials and free radical generate new energy matter---product gas according to the betatopic reaction that gets that thermodynamics can spontaneously carry out again.Phase transformation, that promote by external world's acting, Gibbs function change rising process (Δ G＞0), that chemical reaction equilibrium is moved to the left that whole process takes place, follows in the isothermal open system.The interface of the countless catalyzer/reaction substrates that are dispersed in has constituted numerous " electrode reaction " in the reformer.The loop of the necessary electrons/ions of electrode reaction is set up in microwave plasma, and promptly the intravital electronics of plasma shows the volta effect of inducting under the electrical forces effect.And in plasma body, drive the mass transfer finish between various vapour particles and the process of load transfer by electrical forces.So there are not the various problems of making us perplexing of electrons/ions loop deutero-in the electrode reaction in the narrow and small restriction of both electrodeless conversion zone yet.Usually the electrode reaction hot merit loss doing one's utmost to avoid is here by reasonable use.
With a blunt a little metaphor: whole reformer and content are equivalent to one big " chemical capacitor ", and microwave electric field is being given this big electric capacity " charging " all the time.Because capacitor memory is having impurity (reaction material) gentle (vapour) crack, causes the leakage conductance and the electrical breakdown (plasma discharge) of electric capacity, so finished " dashing-discharge " circulation of electric capacity.Reaction material has been finished by the phase transformation of solid to gas in above-mentioned physicochemical change process.And borrow the output of product gas that chemical equilibrium is moved to the direction of resultant, so formed the successive complete processing.
The reaction mechanism of fused salt semi-conducting electrode (following is example with sodium, and potassium and lithium are in like manner):
Na
2The heat that O forms is given birth to e
-/ h
+Current carrier is Na/O to (semi-conductive electrons/to)
-, can be expressed as:
Na
+Na
+O
2-+ thermal excitation → NaNa
+O
-
The electrochemical relationship formula:
Hole (the h of oxidizing electrode=semi-conductor valence band
+)=O
-
Electronics (the e of reducing electrode=semi-conductor conduction band
-)=Na (Na atom)
Na/O
-Hole (the O that current carrier is right
-) redox potential near+3.0V (level of energy of the 2p electronic orbit of O atom).O
-The oxidation capacity of the catalyst of transition metal oxide that often uses to us of oxidation capacity similar.But the reducing power of Na but has very big difference with our reducing power of the frequent catalyst of transition metal oxide that uses.Such as, Ti
4+/ Ti
3+The right redox potential of electricity is-0.1V, with H
+/ H electricity is nearer to the redox potential of 0V, to H
+Reducing power limited; And Na
+The right redox potential of/Na electricity is-2.71V is to H
+Reducing power just very strong.Compare Na/O with the catalyst of transition metal oxide that we use always
-Current carrier is arranged in pairs or groups relatively more balancedly to all have very dark energy level (approaching the limit) on valence band and conduction band, is a catalytic oxidation-reduction system that is better than all transition metal oxides.
Fused salt catalyzed degradation organism carries out under alkaline condition, and the strong oxidizer of decomposing organic matter is OH.Two electricity that relate to are to being
With
Two relevant " half-reaction " formulas are:
Under alkaline condition, with H
2O is reduced into OH
-Ionic mechanism has two:
①
②
Because body series is not from outside input O
2, O
2Be to come to H
2The reduction of O is at reduction H
2Produce H in the time of O
2Gas.So this reformation gasification system be after a kind of mechanism be main.Two " half-reaction " formulas of this technology are:
③
Net reaction is:
Total reversible electromotive force is: E
θ=-2.8V (0.828V-+1.972V)
E
θFor negative value (2.8V) represents that this is the non-spontaneous reaction of carrying out of thermodynamics.
So two " half-reactions " the forming interval that requires the semiconductor catalyst band gap to cover increase to 2.8V (+1.972+-0.828) more than.And adopt outer for O
2Technology, wide of catalyzer band gap need 1.571V (+1.972-0.401) more than.
Examine and will find, 3. formula is by following 4. formula with after 5. formula merges:
4. water decomposition:
5. organic matter degradation:
If we are under the top alkaline condition, 4 " half-reaction " formulas of this of water decomposition and organic matter degradation relatively will find, in the water decomposition reaction, and OH
-Ion is oxidized to O
2And in the organic matter degradation reaction, OH
-Ion is oxidized to OH.This reformation gasification system is the reaction system that the reaction of water decomposition reaction and organic matter degradation is merged, and 3. organic theoretical decomposition voltage is 2.8V (2.8V=1.972V+0.828V) after the fusion.It is to adopt to supply O outside negative electrode
2The organic theoretical decomposition voltage of mode 5. with the theoretical decomposition voltage of water adding and (2.8V=1.571V+1.229V) 4..That is, above-mentioned organic matter degradation 5. with water decomposition 4. two reaction formula merge (two anodic reactions are placed on same one side of equal sign, and two cathodic reactions are placed on the other side), remove " similar terms " on equal sign both sides then.The implication of removing " similar terms " is: the O that organic matter degradation is required
2Come from the O that water decomposition produces
2The resultant of the oxidation utmost point is strong oxidizer---the OH of organic matter degradation reaction in the system, rather than O
2The resultant of the reduction utmost point is H
2And OH
-The conductive ion that merges between latter two " half-reaction " remains OH
-Certainly, Na/O
-Heat is given birth to current carrier to being more powerful redox couple, but its sphere of action only limits on the contact interface.And OH can be diffused into farther scope, and even among gas/plasma body.
The energy gap of fused salt semiconductor catalyst can significantly be dwindled under the high temperature more than 850 ℃, and the activation overpotential of semi-conducting electrode reaction is declined to a great extent, and levels off to 0V.2.8V be the energy that produces the needed thermodynamic significance of OH, can not save.High temperature more than 850 ℃ can reduce the activation overpotential of semi-conducting electrode reaction, and this is the energy of dynamic significance, is the reflection of activation energy in polarization of electrode, can save.
" active oxygen " species that come from water that participate in decomposing organic matter also have O except OH
2 -, HOO, H
2O
2, O (
1D), O
3, creating singlet oxygen by using etc.The oxidation capacity of these species is not as OH, and the energy consumption that produces them is also not as the OH height.The reaction that these active oxygen species cause subsequently also all is that thermodynamics can the spontaneous thermopositive reaction of carrying out.So though the energy consumption of water of decomposition is higher, the thermopositive reaction of Fa Shenging thereafter can remedy the part energy consumption.Such as:
C+0.5O
2→ CO heat release 110.5kJ/mol
From foregoing description as can be seen, this technology is " thermoelectrochemistry " process that thermochemistry combines with electrochemistry.The main energy consumption of process is in the decomposition that occurs in water.The O that from water electrolysis, obtains in the DC electric field
2Be not used in the carbochain operation that interrupts carbon group compound.Present technique is the O that obtains in the water electrolysis
2" on the spot " use on the decomposing organic matter.Therefore just need not from air, separate O
2Consumed power.Brine electrolysis is just " the equivalent conversion " between electric energy and the chemical energy at the most, the O that present technique will obtain from water decomposition
2Turn to organic oxygenolysis, generate CO, realized the increment of chemical energy.In the product gas owing to increased H
2Content and H
2/ CO ratio more helps the downstream synthetic liquid fuel.
In electromagnetic spectrum, the above frequency spectrum of ultraviolet ray is included into the ionizing rays category.The photon energy of these spectral lines is bigger, can directly act on the outer orbit electronics of atom, makes the electron detachment molecular orbital(MO), and photo-ionisation takes place, and causes chemical bond rupture.And infrared and energy microwave photon is much smaller, especially microwave.Such as, 2.45GHz microwave photon energy is about 10
-5EV, its energy reaches far away by means of photo-ionisation, interrupts the degree of chemical bond.Therefore infrared and microwave belongs to the nonionizing radiation category.Though the photon energy of these two kinds of rays is less, because they are corresponding to the vibrational level and the rotational level of medium, so very strong to the thermal effect that is applied thing.The skin depth of microwave frequency band and the thickness of reactor can only occur in and show very much shallow position and infrared wave etc. are higher than the magnetoresistive effect of the frequency spectrum of microwave on the same order of magnitude.Microwave radiation can be transmitted to the inside of reactor, and the energy that makes valence electron obtain the interorbital transition even de-orbit by thermal excitation, and chemical bond disintegrates because of losing valence electron.Because thermal excitation (radiationless transition) is lattice fluctuation (phonon) coupling through microwave and ionic crystal (fused salt), generate phonon-polariton (phonon-polaritons) ripple, realize by the roundabout process of phonon-polariton excitation electron transition again.Through photon-phonon coupling → phonon-polariton mould → transition of electron, be an auxiliary energy transfer process of multi-phonon (multi-phonon transition), so need certain action time.And ultraviolet photon to act on valence electron be man-to-man DIRECT ENERGY exchange between photon and electronics.Under the normal temperature between ultraviolet photon excitation band crack the speed of the direct transition of electronics usually 10
-15～10
-17About second-time.If calculate according to same power, though the energy of 2.45GHz microwave photon is less than 6 orders of magnitude of near-ultraviolet ray photon, but because its quantum sum in the same time is also greater than 6 orders of magnitude of near ultraviolet photon, so both effect intensity of excitation electron in the same time are the same.The reason of real time expand does not lie in to be to use which kind of radiation means, and the gasification that is to reform is thermo-negative reaction.Average phonon number in the semi-conductor electricity electrode catalyst that thermo-negative reaction consumed needs microwave exposure to recover with the regular hour.In view of photon is by microwave power (amplitude of light wave) decision, so unique factor of conditioned response speed is exactly a microwave power in the probability density of spatial distribution with to the reactive force intensity of electronics.This reformation gasification reaction times design is in the several seconds.And various relevant elementary reaction recited above all is a femtosecond (10
-15Second) order reaction.So, just have time enough to open carbochain fully as long as microwave power is guaranteed.
Embodiment 1:
With fusion yellow soda ash (Na
2CO
3) cause heating bed material as microwave, with diameter less than the wood chip of 0.5cm as processed raw material.The gasification reaction temperature is set in 860 ℃ ± 10 ℃.Reactor inside diameter 50cm, height 240cm, bed of molten salt material height 180cm, gas outlet pressure sentence the x direction of principal axis at height for reactor 160cm and arrange 3 microwave energy-feeding mouths from top to bottom greater than 0.1MPa, and each power input is 6kWh.In addition, at bottom z direction of principal axis 1 microwave energy-feeding mouth is arranged, power input is 6kWh.At reactor head y direction of principal axis 1 microwave energy-feeding mouth is arranged, power input is 6kWh.Totally 5 microwave energy-feeding mouths, total power is 30kWh.Microwave frequency is 2.45GHz.In 1 hour time,, evenly imported 5 kilograms of high-temperature water vapors with 12 kilograms in even velocity input wood chip material.Obtain reformed gas 25m after removing water vapor
3, calorific value 11.5MJ/m
3H wherein
2Account for 59.6%, CO accounts for 29.2%, CO
2Account for 10.3%, other gas 0.9%.
Embodiment 2 (water vapor and pure oxygen are united reformation):
The general reaction condition is identical with embodiment 1.Just the total power of 5 microwave energy-feeding mouths addition is 25kWh.With diameter less than the hard coal of 0.4cm as processed raw material.In 1 hour time, imported 7.5 kilograms of smokeless coal charges, evenly import 8 kilograms of high-temperature water vapors and 1 cubic metre of pure oxygen (1.428 kilograms) with even velocity.Obtain reformed gas 25m after removing water vapor
3, calorific value 11.5MJ/m
3H wherein
2Account for 61%, CO accounts for 28.1%, CO
2Account for 9.8%, other gas 1.1%.
Claims (10)
1, a kind of method of microwave excitation molten salt catalytic reforming gasification carbon group compound, it is characterized in that: with the ceramic material reactor wall of microwave inertia and heat-resisting oxidation, expect the double as catalyzer with fused carbonate as the heating bed, be transported in the reactor as material to be machined with carbon group compound, be passed in the reactor as vaporized chemical with water vapor, from the outside continuously to reactor internal irradiation microwave; Fused carbonate in the reactor is converted into heat energy with electromagnetic energy, and causes the electrodeless discharge reaction, reacts the reformation gasification process of finishing carbon group compound by electrodeless discharge, obtains with H
2With CO, CO
2Reformed gas for main body.
2, the method for microwave excitation molten salt catalytic reforming gasification carbon group compound according to claim 1, it is characterized in that: described fused carbonate is one or more in yellow soda ash, salt of wormwood, the Quilonum Retard, and comprise their precursor, such as above-mentioned three kinds of alkali-metal oxyhydroxide, formate, supercarbonate; Comprise that also above-mentioned three kinds of alkali-metal fused carbonates decompose sodium oxide, potassium oxide, the Lithium Oxide 98min that the back forms.
3, the method for microwave excitation molten salt catalytic reforming gasification carbon group compound according to claim 1, it is characterized in that: described carbon group compound is meant the material that contains carbon in material molecule is formed, and comprises the mixture of hydrocarbon polymer, carbohydrate, simple substance carbon material and various carbon and oxygen, sulphur compound.
4, the method for microwave excitation molten salt catalytic reforming gasification carbon group compound according to claim 1, it is characterized in that: described water vapor and other vaporized chemical are united reformation, other vaporized chemical be purity oxygen, carbonic acid gas or airborne one or more, the oxygen level of being brought into by water vapor accounts for more than 50% of the total oxygen-supplying amount of various vaporized chemicals, mixes the oxygen level that other vaporized chemical of using brings into it and accounts for 0～50%.
5, the method for microwave excitation molten salt catalytic reforming gasification carbon group compound according to claim 1, it is characterized in that: the range of frequency of described microwave is between 300MHz to 300GHz, temperature in the power 〉=5W, reactor is controlled at 650～1100 ℃, and pressure range is at 0.1～1MPa.
6, a kind of equipment of microwave excitation molten salt catalytic reforming gasification carbon group compound as claimed in claim 1, it is characterized in that: in a metal shell (1), be provided with a reactor (2) with the ceramic material of microwave inertia and heat-resisting oxidation, be connected to the pipeline (3) that feeds a plurality of water vapors or other vaporized chemical in the reactor (2), a feeding screw (4) also is connected in the bottom of reactor (2), also be provided with slag-drip opening (7) in the bottom of reactor (2), the top of reactor (2) is communicated with the outlet (5) of reformed gas; Being provided with microwave energy-feeding mouth (6) on metal shell (1) is arranged on and the corresponding position of reactor (2).
7, the equipment of microwave excitation molten salt catalytic reforming gasification carbon group compound according to claim 6 is characterized in that: microwave energy-feeding mouth (6) adopts x axle, y axle, z axle three-dimensional space layout or two-dimensional space layout with respect to the reactor (2) of cylindricality.
8, the equipment of microwave excitation molten salt catalytic reforming gasification carbon group compound according to claim 6, it is characterized in that: the reactor of the ceramic material of microwave inertia and heat-resisting oxidation (2) wall, the stupalith of employing is aluminium sesquioxide pottery, aluminum silicate ceramic, magnesia ceramics.
9, the equipment of microwave excitation molten salt catalytic reforming gasification carbon group compound according to claim 6, it is characterized in that: reactor (2) wall is provided with lagging material outward, mushy structure that material adopts materials such as aluminium sesquioxide pottery, aluminum silicate ceramic, magnesia ceramics, silicon-dioxide to make.
10, the equipment of microwave excitation molten salt catalytic reforming gasification carbon group compound according to claim 6 is characterized in that: metal shell (1) is provided with Cryogenic air import (8) and high temperature air outlet (9), forces the air cooling circulation.
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