CN103100365B - Plasma cracking carbonaceous material reactor system with hollow cathode or double hollow cathodes - Google Patents
Plasma cracking carbonaceous material reactor system with hollow cathode or double hollow cathodes Download PDFInfo
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- CN103100365B CN103100365B CN201110357391.9A CN201110357391A CN103100365B CN 103100365 B CN103100365 B CN 103100365B CN 201110357391 A CN201110357391 A CN 201110357391A CN 103100365 B CN103100365 B CN 103100365B
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Abstract
The invention discloses a plasma cracking carbonaceous material reactor system with a hollow cathode or double hollow cathodes, which comprises a hollow cathode or double hollow cathodes circularly cooled by a cooling medium and an anode circularly cooled by the cooling medium; a working gas inlet; a carbonaceous material and carrier gas feed inlet; a reaction tube connected to the anode; at least one chilled medium inlet located in a lower portion of said reactor tube; and at least one outlet for the quenched products and gases at the bottom or lower portion of the reactor tube, wherein a chamber for generating plasma and/or electric arc is formed between the hollow cathode and the anode, and the generated plasma gases are sufficiently contacted and mixed with carbonaceous material and carrier gas feed entering the chamber from the hollow channel or annular slit of the cathode at or near the highest temperature region of the chamber to initiate pyrolysis. The reactor system of the present invention has very excellent thermal efficiency and high yield of cracked products.
Description
Technical field
The present invention relates to a kind of for cracking containing the carbonaceous material of volatile matter with the high energy efficiency apparatus and method of production high yield pyrolysis product, particularly, relate to and a kind ofly there is the plasma pyrolysis carbonaceous material reactor assembly of hollow cathode or two hollow cathode and utilize the method for this plasma reactor system cracking carbonaceous material, more particularly, a kind of method utilizing this plasma reactor system to produce acetylene is also related to.
Background technology
Usually, carbonaceous material and other compositions, other suitable heat source as known by arcing device or those of ordinary skill in the art together with hydrogen, to make carbonaceous material cracking or pyrolysis.The result of decomposing as carbonaceous material and the product composition that produces depends on the reaction condition of resolver or reaction zone.As everyone knows, some specific reaction condition is conducive to the formation of some specific components, and such as, reaction zone temperature is higher than the formation being conducive to intermediate product acetylene during 1300K, and or close to during 1300K compared with the decomposition of simultaneous acetylene, be also conducive to the formation of acetylene.
Generally speaking, when electric arc is used as thermal source, arc-through gas, as hydrogen, cause gas temperature in very short time, be increased to high temperature.Arc column temperature reaches 8000K ~ 20000K usually.Temperature when gas leaves electric arc is usually at about 2000K ~ 5000K.With this understanding, gas molecule, partial dissociation as possible in hydrogen molecule become hydrogen atom or even H
+or H
-, produce high-temperature plasma gas thus.
Once high-temperature plasma gas, leave electric arc as plasma hydrogen, plasma gas atom or ion, such as hydrogen atom just have the tendency be exceedingly fast recombining into molecule, and if be that like this they will discharge a large amount of heat.Except the sensible heat of plasma gas, the part great majority of above-mentioned heat by heat conduction, convection current and radiation by near the atom of plasma gas or ion or the particles of carbonaceous material that contacts with it absorb, thus cause particles of carbonaceous material by pyrolysis and/or cracking or decomposition, more particularly, particles of carbonaceous material is caused to release its volatile ingredient, i.e. devolatilization.
Known and determine: with the difference of carbonaceous material type, the decomposition of carbonaceous material and the step of devolatilization and condition can great changes have taken place.Before this, because not knowing as how rational cost obtains the pyrolysis product of high yield as the method for acetylene, so gaseous state and liquid carbon material are the pan feedings that people commonly use by Solid carbonaceous material.Gaseous state and liquid pan feeding are easy to process in addition, and lower to the loss of device of arc.
On the other hand, although basic process steps is known, the mode of instruction people as how a kind of high energy efficiency make to come from Solid carbonaceous material some specific cleavage product, as the such as technical process of the maximize yield of acetylene and technique dynamics still may not be perfectly clear.
In the prior art, be the improvement that the maximize yield of some pyrolysis product coming from Solid carbonaceous material is carried out equipment and process, people have done a lot of trial and experiment.
Such as, US3328276 discloses a kind of method that generation is suitable for the plasma beam of cracking reaction, it comprises makes the hydrogen-hydrocarbon gas mixture of corresponding 6-25 the hydrogen atom of each carbon atom by the cooled negative electrode of hollow and the electric arc of direct current whirling motion-stable that maintains between above-mentioned negative electrode and the cooled anode of hollow, the whirling motion chamber passing through around described electric arc with making hydrogen stream, the electric arc operating voltage wherein represented with volt is 5-15 with the ratio of the electric arc operating current represented with ampere.In the cleavage product stream produced by the method, the content of acetylene is up to 14.80 volume %.
US4358629 discloses and a kind ofly decomposes the method that solid carbonaceous material is translated into acetylene.Specifically, this patent instruction people select the operating condition of low cost, high yield.In that patent, advise that carbonaceous material and the heat of gas and the particular value of enthalpy combine with specific particle diameter and reaction time.Above-mentioned all instructions and suggestion contribute to producing acetylene with commercial competitive cost.
In fact, US4358629 describes a kind of arc reactor, and its direction along solid carbonaceous material movement comprises four regions successively, i.e. solid carbonaceous material powder dispersion district, arc region, reaction zone and chill zone.Because described powder is in the thermal inertia that the time of staying is extremely short and described powder is now temporary transient of arc region, the temperature of described powder keeps certainly close to its temperature at entrance, and the gas simultaneously flowed through reaches the high temperature of 8000K.Solid carbonaceous material powder is only heated by heated air stream by heat conduction and convection current at reaction zone.Like this, all electric power is inputted by thin arc region, namely the large energy being enough to described powder temperature to be increased to more than 1800K causes the irrational excessive gathering of energy, and inevitably by the beat exposure too concentrated on the wall of reactor, thus cause reactor wall overheated.About the wall of guard reactor and the heat that must remove near the wall of reactor accounts for the half of whole electric power input, result, a large amount of valuable energy is had to waste.In addition, specific region occurs that high temperature forms great challenge to the design of reactor wall structure, the selection of wall material, also makes wall protection become a difficult problem.
" pyrolysis of coal in hydrogen and helium gas plasma " (Baumann, H., Bittner, D., Beiers, H.G., Klein, J. & Juntgen, H, Fuel, 1988, Vol.67, pp 1120-1123, and " pyrolysis in hydrogen gas plasma of some gaseous states and liquid hydrocarbon " (Beiers August), H.G., Baumann, H., Bittner, D., Klein, J.and Juntgen, H, Fuel, 1988, Vol.67, pp 1012-1016, July) a kind of equipment being described to carry out coal or gaseous state and liquid hydrocarbon pyrolysis is disclosed, it comprises a plasma generator and a plasma reactor.In the apparatus, it is the high temperature gas flow of 3300K that plasma generator produces in output mean temperature, and this air-flow is introduced in the reaction tube as reactor from top entry subsequently.Dry pulverized coal or gaseous state and liquid hydrocarbon are injected into reaction tube from its side entry near top entry, and wherein cold coal dust is estimated fully to mix with above-mentioned hot plasma air-flow.But, due to plasma flow high-speed downstream, and the strong obstacle therefore formed fluid-powder mixing, to such an extent as to contact between coal dust and plasma flow and heat transfer efficiency are weakened, and the performance of reactor is had a negative impact, simultaneously this structure of reactor and pan feeding arrangement causes almost cannot avoiding coking phenomenon, because coal dust or gaseous state and liquid hydrocarbon wash away the wall surface with knock-on reaction device continuously.
CN1562922 discloses a kind of reactor be similar to described by above-mentioned article, but be the introduction of and be sprayed in reaction tube to prevent the argon gas of reaction tube coking, but reactor disclosed in this patent document does not still overcome above-mentioned all technological deficiencies.
US4536603 discloses a kind of coal and thermal current reacts the method for producing acetylene, the method comprises the following steps successively: under the condition of temperature-controllable, make fuel, oxygen and steam reaction, thus generate and mainly comprise hydrogen, carbon monoxide and water vapour and have a small amount of carbon dioxide, substantially there is no O, OH and O
2thermal current.Described thermal current is raised speed and high velocity impact graininess bituminous coal or ub-bituminous coal logistics, and then the speed of the mixture of hot gas and coal is reduced to about 150-300 feet per second.Control the stream sizes of particulate coal and hot gas, be about the pressure of 10-100pisa to be formed at reaction zone and be about the temperature of 1800-3000 °F.The mixture of coal and hot gas is maintained at about 2-30 millisecond under above-mentioned pressure and temperature, thus generates the product stream comprising burnt and acetylene.The temperature of product stream is brought down below about 900 °F within the time being less than 2 milliseconds subsequently, so that the reaction further of basic termination, and from wherein reclaiming acetylene.Reclaim burnt and used as producing the fuel of hot gas at least partially.
US 4588850 discloses a kind of electric arc or plasma method produces the method for acetylene and synthesis gas or reducibility gas by coal, and the coal wherein powdered is 1-5kWh/Nm in a kind of energy density
3, the time of staying is 0.5-10 millisecond, temperature is by pyrolysis in the arc reactor of at least 1500 DEG C, the quantity of the gaseous compound derived by coal is like this no more than 1.8 times of the quantity of so-called volatile matter in coal.After Quench subsequently, remaining Jiao is fed in the second arc reactor, wherein by means of gasifying medium and in conjunction with electric arc or plasma method heating, Jiao is converted into synthesis gas or reducibility gas wherein, and the time of staying is 1-15 millisecond to Jiao in the reactor, and burnt temperature is at least 800 DEG C.Air-flow from pyrolysis zone is cleaned, and with selective solution from wherein reclaiming acetylene.Gas after purifying step is cooled equally and purify.
CN101742808 discloses and a kind ofly can replace the high-power V shape plasma generator of conventional linear plasma generator, and it claims to have lower energy consumption and operating condition easily.Described V-arrangement plasma generator can be used for producing various high-temperature plasma gas, such as plasma hydrogen and inert gas.
US4367363 discloses and is a kind ofly converted into from coal the method reclaiming pure acetylene in the gaseous state output gas flow produced the method for acetylene.Described gaseous state output gas flow passed through HCN and H in the acid gas stage of removing
2s is adsorbed on organic solvent, as in 1-METHYLPYRROLIDONE, and to rinse with caustic, as NaOH to remove CO
2and by preliminary treatment.In second stage, rinse described gaseous state output gas flow with organic solvent, thus the process of processed gas is provided and is separated pure acetylene product.In the phase III, through the gas of second stage process first by hydrogenation, be desulfurized subsequently and methanation process.The output gas flow processed through the phase III is recycled coal and is converted in the process of acetylene.In fourth stage, the organic solvent from second stage is purified and is recycled in first stage and/or second stage.
The disclosure of all above-mentioned bibliography is introduced with for referencial use in full at this.
In the above-mentioned introduction to prior art with in describing, to those skilled in the art, clearly for cracking or a lot of defect being badly in need of solving of pre-existing reactors existence of decomposing carbonaceous material.Such as, when needing reaction temperature and/or the time increasing or optimize carbonaceous material powder according to pyrolysis product, reaction temperature required by the maximum yield of acetylene, the structure of pre-existing reactors cannot make reaction temperature and/or time make random adjustment.Hot stream temperature declines rapidly along pre-existing reactors longitudinal direction, causes for making the maximize yield reaction gas flow of pyrolysis product must by Quench in shorter displacement, and it is very limited therefore to make carbonaceous material become the conversion of pyrolysis product.As previously mentioned, serious energy waste and Temperature Distribution too high near reactor wall are also do not allow unheeded serious technical problem simultaneously.
In the plasma reactor disclosed in above-mentioned all existing documents and cleavage method thereof, carbonaceous material contact with plasma flow and the region that mixes all away from the highest temperature zone formed by electric arc, this will cause hot transfer efficiency greatly to reduce, also make the gas-phase reaction temperature of the operating temperature of carbonaceous material pyrolysis and devolatilization and volatile matter subsequently greatly reduce simultaneously, and then reduce the productive rate of pyrolysis product, and the thermal efficiency of reactor is also reduced greatly, also likely cause reactor wall and neighbouring overheated and energy waste thereof simultaneously.
The following describes to represent and be specifically related to thermal decomposition and contain the solid carbonaceous material of volatile matter to make some reactor from the maximize yield of the specific cleavage product of solid carbonaceous material and the new understanding of method.Meanwhile, further provide heat solid particles of carbonaceous material as quickly as possible to decompose the described particle of release volatile matter as quickly as possible, thus avoid those volatile matter generation secondary responses in solid carbonaceous particles and form burnt necessary technological parameter.
On the basis of above-mentioned analysis, by countless trial and experiment, the present inventor finally invented almost solve in above-mentioned all defect, such as carbonaceous material fine powder and the highest temperature region of plasma flow near arc column or the good contact realized near it each other and mixing for cracking or the new equipment decomposing solid carbonaceous material, i.e. working mechanism and the plasma reactor system that fluid in existing plasma reactor-powder hybrid concept is greatly different.
Summary of the invention
First aspect present invention provides a kind of plasma pyrolysis carbonaceous material reactor assembly with hollow cathode, comprising:
The hollow cathode of cooled medium circulation cooling and the anode of cooled medium circulation cooling, form the chamber that produces plasma and/or electric arc between described hollow cathode and anode;
Working gas entrance between described hollow cathode outer surface and described anode inner surface, enters in above-mentioned chamber for making described working gas;
Carbonaceous material and carrier gas pan feeding entrance, be positioned at described hollow cathode one end in the cavity, hollow channel in described hollow cathode is used as the transfer passage of carbonaceous material and carrier gas pan feeding, and carbonaceous material and carrier gas pan feeding enter in above-mentioned chamber through above-mentioned transfer passage by carbonaceous material and carrier gas pan feeding entrance;
The reaction tube be connected with above-mentioned anode;
At least one is positioned at above-mentioned reaction tube bottom for Quench or the shock chilling medium entrance freezing product; With
At least one is positioned at bottom above-mentioned reaction tube or the Quench product of bottom and the outlet of gas,
Wherein, described working gas is through the electric arc forming region between described hollow cathode and anode, thus generation plasma gas, and the plasma gas produced is in the highest temperature region of above-mentioned chamber or contact fully with carrier gas pan feeding with the carbonaceous material entering above-mentioned chamber from negative electrode hollow channel near it and mix, and causes pyrolysis.
Second aspect present invention provides a kind of plasma pyrolysis carbonaceous material reactor assembly with two hollow cathode, comprising:
Two hollow cathode of cooled medium circulation cooling and the anode of cooled medium circulation cooling, the chamber that one produces plasma and/or electric arc is formed between one of any and anode of described pair of hollow cathode, one of them hollow cathode is positioned at the hollow channel of another hollow cathode, forms anchor ring slit between two hollow cathodes;
Working gas entrance between described pair of hollow cathode outmost surface and described anode inner surface, enters in above-mentioned chamber for making described working gas;
Carbonaceous material and carrier gas pan feeding entrance, be positioned at described pair of hollow cathode one end in the cavity, the described anchor ring slit of described pair of hollow cathode or innermost hollow channel are used as the transfer passage of carbonaceous material and carrier gas pan feeding, and carbonaceous material and carrier gas pan feeding enter in above-mentioned chamber through above-mentioned transfer passage by carbonaceous material and carrier gas pan feeding entrance;
The reaction tube be connected with above-mentioned anode;
At least one is positioned at above-mentioned reaction tube bottom for Quench or the shock chilling medium entrance freezing product; With
At least one is positioned at bottom above-mentioned reaction tube or the Quench product of bottom and the outlet of gas,
Wherein, described working gas is through the electric arc forming region between one of described pair of hollow cathode and anode, thus generation plasma gas, and the plasma gas produced is in the highest temperature region of above-mentioned chamber or contact fully with carrier gas pan feeding with the carbonaceous material entering above-mentioned chamber from the anchor ring slit of two hollow cathode or innermost hollow channel near it and mix, and causes pyrolysis.
According to the present invention first and/or second aspect, in above-mentioned plasma reactor system, preferably, the described anchor ring slit of described pair of hollow cathode or innermost hollow channel are used as the transfer passage of the preheating gas of working gas or preheating carbonaceous material and carrier gas pan feeding, and their bottom is used as the entrance of the preheating gas of working gas or preheating carbonaceous material and carrier gas pan feeding; Nearest horizontal range between described hollow cathode outer surface and the inner surface of described anode is 1-400 millimeter; And the minimum distance between described hollow cathode outer surface lower end and the inner surface of described anode is 1-400 millimeter, is preferably 1-15 millimeter; The inner surface forming range of described anode side walls and diapire is 90 °-160 °, is preferably the angle of 105 °-145 °; At least part of region of described hollow cathode outer surface and anode outer surface is cooled medium circulation cooling, has cooling medium entrance and cooling medium outlet near it; The temperature entering the preheating gas in the described anchor ring slit of described pair of hollow cathode or innermost hollow channel is 100-1000 DEG C; The lower end of described anchor ring slit or the lower end of innermost hollow channel of the lower end of described hollow cathode, two hollow cathode are connected with logistics distributor, in order to regulate flow velocity or the flow direction of carbonaceous material and carrier gas pan feeding, working gas and/or preheating gas.
Equally preferably, the temperature of described chamber highest temperature region guarantees that the temperature of the carbonaceous material entered wherein or in its vicinity reaches 650 DEG C ~ 1250 DEG C, and carbonaceous material temperature after entering described reaction tube reaches 1500 DEG C ~ 2900 DEG C; Described working gas is becoming the high-temperature plasma gas of hydrogen, nitrogen, methane and/or inert gas after electric arc forming region; Described preheating gas is the plasma gas of hydrogen, nitrogen, methane, inert gas and/or hydrogen, nitrogen, methane and/or inert gas; The shock chilling medium entered in described reaction tube guarantee product before leaving reaction tube by Quench to lower than 527 DEG C; The time of staying of carbonaceous material in described reaction tube is 0.4 ~ 4.0 millisecond; In described reactor assembly, there is carbonaceous material pyrolysis, the temporal summation of volatile matter gas-phase reaction and pyrolysis product Quench is less than 50 milliseconds; Described shock chilling medium comprises water, steam, propane, aromatic compound, inert gas, the carbonaceous material of any type and/or their mixture; Described carrier gas is selected from hydrogen, nitrogen, methane, gaseous carbon material, inert gas and/or their mixture; The cross section of described anode and/or reaction tube is circular, square, oval, polygon or any other regular shape; The area ratio of described reaction tube top and bottom cross section is 1/1-1/3.
Still preferably, the entry number of described carbonaceous material and carrier gas pan feeding is 1 ~ 32, and the entry number of described working gas is 2 ~ 32, and the entry number of described shock chilling medium is 2 ~ 64; The entry number of described preheating gas is 1 ~ 32; Described various entrance is in the horizontal direction by symmetrical and/or relatively arrange;
Described carbonaceous material is selected from coal, coal tar, coal directly-liquefied residue, heavy oil residue, Jiao, petroleum coke, oil-sand, shale oil, carbonaceous industrial waste or tailing, living beings, synthetic plastic, synthetic polymer, damaged tire, Municipal solid rubbish, pitch and/or their mixture; The input power of described hollow cathode and/or anode is 10kW ~ 20MW, to form the electric arc producing plasma gas; The entrance of described working gas and/or the entrance of shock chilling medium are centrosymmetric distribution in the horizontal direction; The entrance of described shock chilling medium in the horizontal direction forming range is the angle of-45 ° to+45 °; Two in the horizontal direction relatively or the entrance of directly not relative described shock chilling medium vertically shape is at an angle; The volume ratio of carbonaceous material and carrier gas is 10/90 ~ 90/10; Pyrolysis product comprises acetylene, carbon monoxide, methane, ethene and Jiao; The average grain diameter of carbonaceous material is 10 ~ 300 microns.
Accompanying drawing explanation
Fig. 1 is the representative schematic diagram that the present invention has the plasma reactor system of hollow cathode.
Fig. 2 to contact with plasma flow and the schematic diagram of Mixed Zone for carbonaceous material in the plasma reactor system shown in Fig. 1.
Fig. 3 is the representative schematic diagram that the present invention has the plasma reactor system of two hollow cathode.
Detailed description of the invention
Be further explained in detail the present invention by description below with reference to the accompanying drawings, the corresponding or equivalent parts wherein shown in accompanying drawing or the identical reference numerals of feature represent.
Generally speaking, the reaction of the volatile matter discharged by RESEARCH OF PYROCARBON material, such as bituminous coal plays a part necessary and important in pyrolysis product is produced.Due to carbonaceous material experience and the gas of high reaction activity, the reaction be exceedingly fast of such as high-temperature plasma gas, and such reaction requires to be terminated instantaneously, to such an extent as to cannot describe with common process or calculate above-mentioned pyrolysis and reaction.Broadly, pyrolysis product distribution depends on the type of carbonaceous material and the operating condition of employing, if reaction and/or the time of staying only have several milliseconds, the sufficient time just can not be had to reach thermodynamic equilibrium, and therefore would not generate can the cigarette ash that formed of the volatile matter secondary response produced by carbonaceous material of quantitation.
For solid carbonaceous material, the heat transfer of carbonaceous material and pyrolysis, homogeneous phase be solid-and solid/liquid/gas reactions and homogeneous gas phase all can affect speed, the i.e. productive rate that pyrolysis product is formed.In fact, one of main purpose of the present invention is exactly make some specific cleavage products, maximize yield as acetylene, therefore understands and determine that the characteristic of above-mentioned pyrolysis and reaction, mechanism and operating condition have been keys of the present invention.
Countless test and observation confirm: the pyrolysis temperature of carbonaceous material, particularly solid carbonaceous material is preferably 650 DEG C ~ 1250 DEG C, such as 680-1100 DEG C, be more preferably 700 DEG C ~ 930 DEG C, be particularly preferably 750 DEG C ~ 900 DEG C, such as 850 DEG C, and the gas-phase reaction temperature of the volatile matter obtained by carbonaceous material is preferably 1500 DEG C ~ 2900 DEG C, is more preferably 1500 DEG C ~ 2500 DEG C, being particularly preferably 1500 DEG C ~ 2000 DEG C, such as, is 1750 DEG C or 1850 DEG C.
Said temperature determine carbonaceous material experience pyrolysis and discharge volatile matter preferable temperature and subsequently volatile matter carry out the preferable temperature of gas-phase reaction.Because carbonaceous material pyrolysis is formed in the chamber producing plasma and/or electric arc and just starts between described hollow cathode and anode, and estimate that the volatile matter exceeding maximum growing amount 60% is formed in above-mentioned chamber, the gas-phase reaction of above-mentioned volatile matter then mainly occurs in reaction tube.
Desirable fast as far as possible and transform as far as possible completely in order to obtain, the above-mentioned gas-phase reaction time of described volatile matter is preferably less than 4 milliseconds, such as 2 milliseconds, more preferably less than 1 millisecond, is particularly preferably less than 0.4 millisecond, such as, is less than 0.3 or 0.2 millisecond.Such reaction time can ensure the high yield obtaining pyrolysis product.
Generally speaking, the feasible method improving the productive rate of pyrolysis product, particularly acetylene has following several:
First, elementary volatile matter and at high-temperature plasma gas, as plasma hydrogen and/or comprise the high but reaction height be exceedingly fast between the plasma composition that the time-to-live is short of reactivity in the inert gas of helium and control some specific cleavage product, productive rate as acetylene.Therefore, if extremely fast RESEARCH OF PYROCARBON material and discharge high concentration or a large amount of volatile matters, the productive rate of pyrolysis product will be higher, this ultra-fine grain diameter by choose reasonable carbonaceous material distributes, or consider that the oxygen in volatile matter can be converted into carbon monoxide and consume acetylene, adopt the low-grade but carbonaceous material that oxygen content is low to realize.
Secondly, the optimum operation condition of RESEARCH OF PYROCARBON material is selected, to obtain the volatile matter of maximum quantity.Therefore, suitable pyrolysis time, pressure and/or temperature make described volatile matter growing amount reach maximum key.
3rd, above-mentioned volatile matter is contacted with the plasma composition of as far as possible many high reaction activities, so does and can increase reaction surface and improve reaction conversion ratio.
4th, the reaction temperature of volatile matter and high reaction activity plasma composition is another key factor affecting pyrolysis product productive rate, generally speaking, the productive rate of pyrolysis product improves with the temperature of above-mentioned gas-phase reaction and increases, but too high reaction temperature can cause being formed can the cigarette ash of quantitation and hydrogen.
Those of ordinary skill in the art can obviously find out from above analysis: the pyrolysis of carbonaceous material and the gas-phase reaction of elementary volatile matter and high reaction activity plasma composition are all the most important processes forming pyrolysis product.But, the optimal processing parameter of pyrolysis or operating condition are usually different from the optimal processing parameter of above-mentioned gas-phase reaction or operating condition, if as the structural design of the plasma reactor existed in prior art, i.e. the contacting and mixing of carbonaceous material and plasma flow, carbonaceous material pyrolysis, occur in the same space or region with volatile matter gas-phase reaction, not only because the region that carbonaceous material contacts with plasma flow and mix causes hot transfer efficiency to decline away from high-temperature region, and the technological parameter of pyrolysis and gas-phase reaction or operating condition also cannot reach well balance and optimization.
For above-mentioned fatal shortcoming, the present inventor is proposed by countless trial and experiment and has been invented a kind of plasma reactor system of brand new, the plasma reactor system invented makes above-mentioned pyrolysis and gas-phase reaction occur at least in part in different spaces or region dexterously, thus makes the technological parameter of pyrolysis and gas-phase reaction or operating condition reach optimum simultaneously.
In detail, as shown in Figure 1-2, described plasma reactor system comprises:
The hollow cathode 11 of cooled medium circulation cooling and the anode 5 of cooled medium circulation cooling, form the chamber that produces plasma and/or electric arc between described hollow cathode and anode;
Working gas entrance between described hollow cathode 11 outer surface and described anode 5 inner surface, enters in above-mentioned chamber for making described working gas 4;
Carbonaceous material and carrier gas pan feeding entrance, be positioned at described hollow cathode 11 one end in the cavity, hollow channel in described hollow cathode 11 is used as the transfer passage of carbonaceous material and carrier gas pan feeding 1, and carbonaceous material and carrier gas pan feeding 1 enter in above-mentioned chamber through above-mentioned transfer passage by described carbonaceous material and carrier gas pan feeding entrance;
The reaction tube 14 be connected with above-mentioned anode 5;
At least one is positioned at above-mentioned reaction tube 14 bottom for Quench or the entrance of shock chilling medium 8 freezing product 10; With
At least one is positioned at bottom above-mentioned reaction tube 14 or the Quench product 10 of bottom and the outlet of gas,
Wherein, described working gas 4 is through the electric arc forming region 20 between described hollow cathode 11 and anode 5, thus generation plasma gas, and the plasma gas produced is in the highest temperature region 21 of above-mentioned chamber or contact fully with carrier gas pan feeding 1 with the carbonaceous material entering above-mentioned chamber from negative electrode hollow channel near it and mix, and causes pyrolysis.
The structural design of above-mentioned plasma reactor system makes in the chamber of formed plasma flow between above-mentioned hollow cathode and anode, particularly in the highest temperature region of the contiguous arc column of described chamber or near to contact fully with carrier gas pan feeding with carbonaceous material and mix, pyrolysis is caused fast and while efficient heat transfer in realization, and start to discharge volatile matter, along with the lasting of heat transfer and mixture enter in the reaction tube below described chamber, carbonaceous material and the volatile matter temperature formed promote further, and cause the gas-phase reaction of volatile matter, thus produce various pyrolysis product, like this, the technological parameter of pyrolysis and gas-phase reaction and operating condition can be controlled independently of one another or be selected, also make them be optimised simultaneously and become possibility, in any case this structural design being existing plasma reactor is also beyond one's reach.
In another preferred embodiment of the present invention, above-mentioned hollow cathode can replace by two hollow cathode, as shown in Figure 3, described pair of hollow cathode comprises two hollow cathodes 11 and 19, one of them hollow cathode 19 is positioned at the hollow channel of another hollow cathode 11, anchor ring slit is formed between two hollow cathodes 11 and 19, the one of any of described pair of hollow cathode can form the chamber that produces plasma and/or electric arc between 11 or 19 and anode 5, carbonaceous material and carrier gas pan feeding can or enter in above-mentioned chamber from above-mentioned anchor ring slit from the hollow channel of innermost hollow cathode 19, now, the lower end of the lower end of described anchor ring slit or the hollow channel of hollow cathode 19 is by the entrance as carbonaceous material and carrier gas pan feeding.
Above-mentioned pair of hollow cathode benefit is used to be: when carbonaceous material and carrier gas pan feeding 1 enter described chamber from described anchor ring slit, under hollow cathode 19 inside or the hollow cathode 11 of outside are used as the condition of work negative electrode, namely the hollow channel of the hollow cathode 19 of the inside can be used as the supplementary passage of working gas 4, also can be used as transfer passage carbonaceous material and carrier gas pan feeding 1 being carried out to the hot gas 15 of preheating, thus make carbonaceous material and carrier gas pan feeding carry out contacting front temperature with plasma flow can be higher, this is conducive to fast and heat transfer efficiently.Under just hollow cathode 19 is inside used as the condition of work negative electrode, carbonaceous material is the same with working gas 4 with carrier gas pan feeding 1, also arc column can be passed, it is with before produced plasma flow carries out contacting and mix, by described arc column preheating or heated, like this, the temperature of carbonaceous material or will be higher by firing rate, thus be conducive to the release of more volatile matters.
Another benefit of above-mentioned pair of hollow cathode is used to be: when the hollow channel of carbonaceous material and carrier gas pan feeding 1 hollow cathode 19 from the inside enters in described chamber, under hollow cathode 19 inside or the hollow cathode 11 of outside are used as the condition of work negative electrode, namely described anchor ring slit can be used as the supplementary passage of working gas 4, also can be used as the transfer passage of the hot gas 15 carbonaceous material and carrier gas pan feeding being carried out to preheating, thus make carbonaceous material and carrier gas pan feeding 1 carry out contacting front temperature with plasma flow can be higher, this is equally also conducive to fast and heat transfer efficiently.Just hollow cathode 19 is inside used as under work negative electrode and described anchor ring slit be used as the condition of supplementary passage of working gas 4, and the working gas 4 entered described chamber from described anchor ring slit equally also can produce high-temperature plasma air-flow through arc column.
As Figure 1-3, the position of electric arc forming region 20 and/or highest temperature zone 21 can be changed by the position of adjustment described hollow cathode, two hollow cathode, anode and/or described chamber, size and/or structural parameters, such adjustment can guarantee carbonaceous material and carrier gas pan feeding 1 and plasma flow carry out fully and high-efficient contact and the region that mixes be positioned at described chamber be close to the highest temperature zone 21 of electric arc forming region 20 or its near, thus realize fast and to conduct heat efficiently.Such as, described hollow cathode 11 or one of any nearest horizontal range d between 11 or 19 outer surfaces and the inner surface of described anode 5 of two hollow cathode
1or d
3be generally 1-400 millimeter; And described hollow cathode 11 or one of any minimum distance d between 11 or 19 outer surface lower ends and the inner surface of described anode 5 of two hollow cathode
2or d
4be generally 1-400 millimeter, be preferably 1-15 millimeter, such as 10 millimeters; The sidewall 13 of described anode 5 and the inner surface forming range of diapire 9 are generally 90 °-160 °, are preferably the angle of 105 °-145 °, such as 135 °.
In order to prevent hollow cathode, two hollow cathode and/or anode overheated, at least part of region of described hollow cathode 11 and 19 outer surface and anode 5 outer surface is cooled medium circulation cooling, has cooling medium entrance 2,17 and 6 and cooling medium outlet 3,18 and 7 near it.Physical isolation is carried out by insulating element 12 between hollow cathode 11 and 19 and anode 5.The temperature entering the hot gas 15 of preheating carbonaceous material and carrier gas pan feeding 1 in the described anchor ring slit of described pair of hollow cathode or innermost hollow channel is generally 100-1000 DEG C.
Preferably, to contact with material high-efficiency to realize flash heat transfer most effectively and to mix, the lower end of described anchor ring slit between the lower end of described hollow cathode 11, two hollow cathode 11 and 19 or the lower end of the hollow channel of innermost hollow cathode 19 are optionally connected with logistics distributor 16, in order to regulate flow velocity or the flow direction of carbonaceous material and carrier gas pan feeding 1, working gas 4 and/or preheating gas 15.
In above-mentioned plasma reactor system, pyrolysis temperature is generally 650 DEG C ~ 1250 DEG C, gas-phase reaction temperature is then 1500 DEG C ~ 2900 DEG C, so pyrolysis temperature is significantly less than gas-phase reaction temperature, for promoting that the preheating gas 15 of pyrolysis can be the plasma gas of hydrogen, nitrogen, methane, inert gas and/or hydrogen, nitrogen, methane and/or inert gas, and working gas 4 is at the high-temperature plasma gas becoming hydrogen, nitrogen, methane and/or inert gas after electric arc forming region 20.
In order to prevent from being obtained by gas-phase reaction pyrolysis product, as acetylene decomposition or cigarette ash and the hydrogen that secondary response finally forms low value occurs, the pyrolysis product generated must instantaneously by Quench leaving described reaction tube 14 before.Generally speaking, pyrolysis product after it is formed preferred within 4 milliseconds, such as 2 millisecond by Quench to 650 DEG C, preferably 600 DEG C, particularly preferably less than 527 DEG C.Described shock chilling medium can preferably include water, water vapour, propane, aromatic compound, inert gas, the carbonaceous material of any type and/or their mixture.
The pressure of described reactor assembly can be negative pressure-malleation, such as 70 ~ 200KPa, preferably 100 ~ 150KPa, more preferably 110 ~ 140KPa.The length of reaction tube 14 and pan feeding flow typically depend on the time of staying of pan feeding in reaction tube 14 and reaction time.More typically, the temporal summation of the pyrolysis occurred in described reactor assembly, gas-phase reaction and Quench is preferably less than 50 milliseconds.
In order to obtain ultra-fine grain or finely disseminated carbonaceous material excellent transmission efficiency and/or realize fully mixing or close contact of carbonaceous material and plasma flow, usual needs are for transmitting the carrier gas of carbonaceous material, and carrier gas can be selected from hydrogen, methane, nitrogen, gaseous carbon material, inert gas and/or their mixture.The exemplary embodiment of inert gas is such as argon gas and/or helium.
The cross section of described anode 5 and reaction tube 14 is any shape, such as circular, square, oval, polygon or any other regular shape.But in order to prevent reaction tube 14 inner wall surface from obvious coking occurring, the cross-sectional area of described reaction tube 14 lower end is preferably 1 ~ 3 times of the cross-sectional area of its upper end.Such design prevents pan feeding or pyrolysis product directly to wash away above-mentioned inner surface and is formed thereon or build up burnt.
Equally, in order to distribute equably in described reactor assembly inner space or dispersion pan feeding 1, working gas 4, preheating gas 15, pyrolysis product 10 and/or shock chilling medium 8, preferably: the entry number of carbonaceous material and carrier gas is 1 ~ 32, the entry number of working gas is 2 ~ 32, and the entry number of shock chilling medium is 2 ~ 64, the entry number of preheating gas is 1 ~ 32, and it is even more preferred that above-mentioned entrance is in the horizontal direction by symmetrical and relatively arrange.
The carbonaceous material used in plasma reactor system of the present invention can be solid-state, liquid and/or gaseous material, and be preferably solid carbonaceous material, such as, it is selected from coal, coal tar, coal directly-liquefied residue, heavy oil residue, Jiao, petroleum coke, oil-sand, shale oil, carbonaceous industrial waste or tailing, living beings, synthetic plastic, synthetic polymer, damaged tire, Municipal solid rubbish, pitch and/or their mixture.
In plasma reactor system of the present invention, the input power of described hollow cathode 11 or 19 and/or anode 5 is 10kW ~ 20MW, to form the electric arc producing plasma flow.The details relevant to plasma generator can be taken from or such as, with reference to aforementioned reference, US4358629, CN1562922A or CN 101742808A, in order to save space, and being described in detail in this and saving about plasma generator.
Owing to just starting in the chamber that carbonaceous material pyrolysis is formed between above-mentioned hollow cathode 11 or 19 and anode 5, and to enter after in reaction tube 14 still in continuation, so its time is usually high than the reactivity contained by the main elementary volatile matter occurred in reaction tube 14 and high-temperature plasma air-flow but the time that the is gas-phase reaction of the plasma composition that the time-to-live is short is long.
In order to distribute equably in above-mentioned chamber or in reaction tube 14 working gas 4 or shock chilling medium 8, the entrance of described working gas 4 and/or the entrance of shock chilling medium 8 are preferably centrosymmetric distribution in the horizontal direction, particularly, the entrance of described shock chilling medium 8 can forming range be the angle of-45 ° to+45 ° in the horizontal direction, and two in the horizontal direction relatively or the entrance of directly not relative described shock chilling medium 8 optionally vertically shape is at an angle, to obtain pyrolysis product 10, the particularly best chill effect of fresh acetylene, thus make their productive rate reach maximum.
The above-mentioned novel structure design of plasma reactor system of the present invention has the following advantages and feature:
First, the region contacted with plasma flow due to carbonaceous material and carrier gas pan feeding 1 and mix to close at above-mentioned chamber in the highest temperature region 21 of electric arc forming region 20 or near, temperature and its of carbonaceous material are greatly improved by firing rate, while realizing quick and efficient heat transfer, carbonaceous material has discharged more volatile matter, and this is conducive to forming more pyrolysis product.
Secondly, carbonaceous material pyrolysis just starts in above-mentioned chamber, and be continued until that it enters after in reaction tube, therefore carbonaceous material and high-temperature plasma air flow contacts, the time of mixing and pyrolysis is different with region or incomplete same from the time of the elementary volatile matter gas-phase reaction mainly occurred in reaction tube with region, this will make pyrolysis and gas-phase reaction occur in different spaces or region at least in part, thus the technological parameter of pyrolysis and gas-phase reaction or operating condition may be regulated and controled independently of one another, and reach optimum simultaneously, this becomes the conversion ratio of pyrolysis product by greatly improving carbonaceous material.
3rd, because achieve carbonaceous material and quick and efficient heat transfer between carrier gas pan feeding and plasma flow, and, carbonaceous material and high-temperature plasma air flow contacts, the region that mixes are in above-mentioned chamber, instead of in reaction tube, avoiding problems serious energy waste and near reaction tube, occur coking and too high Temperature Distribution, result, the concentrations of Thermal release there will not be in reaction tube.
Plasma reactor system of the present invention can be used to produce the pyrolysis product from various carbonaceous material, and typical method is as described below:
A) through the hollow channel of described hollow cathode, carbonaceous material is incorporated in the chamber of generation plasma and/or the electric arc formed between hollow cathode and anode by means of carrier gas;
B) through the working gas entrance between hollow cathode outer surface and anode inner surface, working gas is incorporated in above-mentioned chamber, working gas subsequently when passing through the electric arc forming region between hollow cathode and anode by plasma, and in the highest temperature region of above-mentioned chamber or contact fully with carrier gas pan feeding with the carbonaceous material entering above-mentioned chamber from hollow cathode hollow channel or anchor ring slit near it and mix, and cause pyrolysis;
C) mixture of carbonaceous material and carrier gas pan feeding and plasma flow enters in reaction tube subsequently, wherein along with the continuation of heat transfer, gas-phase reaction is there is in the volatile matter that pyrolysis produces in reaction tube, optionally, carbonaceous material continues by pyrolysis under the further heat effect of high-temperature plasma air-flow, thus produces cracking and/or thermal decomposition product;
Shock chilling medium is introduced in described reaction tube by the entrance d) through described shock chilling medium, so that Quench or freeze described cracking and/or thermal decomposition product;
E) through the outlet of Quench product and gas by cracking and/or thermal decomposition product, gas, and/or the carbonaceous material residue of pyrolysis discharges described reaction tube.
Generally speaking, the pyrolysis product of carbonaceous material is mixture, and it comprises acetylene, carbon monoxide, methane, ethene, hydrogen and Jiao etc., if want to obtain some specific cleavage product, as acetylene, just need the mixture being separated described pyrolysis product, to obtain substantially pure pyrolysis product.Such as, aforementioned reference US 4367363 discloses the separation method isolating pure acetylene from above-mentioned cleavage product mixtures.In order to save space, be described in detail in this save about what be separated.
In order to obtain the optimum efficiency of carbonaceous material pyrolysis and cracking, except the structural design of plasma reactor system, also should further consider or select the physics and chemistry character of pan feeding, to make the productive rate of pyrolysis product reach maximum.Generally speaking, the average grain diameter of carbonaceous material is preferably 10 ~ 300 microns, and carbonaceous material temperature before entering described reactor assembly is preferably 20 ~ 300 DEG C.The volume ratio of carbonaceous material and carrier gas is generally 10/90 ~ 90/10, is preferably 20/80 ~ 80/20, is more preferably 30/70 ~ 70/30, is particularly preferably 40/60 ~ 60/40, such as 50/50.
Finally, also should be clear: carbonaceous material is preferably greater than 10 by the speed heated in above-mentioned chamber
4k/ second, and in order to the flexibility that operates with under various circumstances to the different demands of operation, the position of described hollow cathode, two hollow cathode, anode and/or described chamber, size and/or structural parameters are adjustable.
Embodiment
Embodiment 1
The reactor assembly of the coal plasma pyrolysis that its schematic diagram is expressed in FIG is used to coal is converted into acetylene and other chemicals.The hollow cathode of described plasma reactor system and/or the input power of anode are 10kW, to form the electric arc producing plasma.As shown in Figure 1, the entrance of described reactor assembly primarily of the entrance of hollow cathode 11, anode 5, working gas 4, reaction tube 14, shock chilling medium 8 and the outlet composition of the cold product 10 of Quench, the nearest horizontal range d between the inner surface of wherein hollow cathode 11 outer surface and described anode 5
1it is 12 millimeters; Minimum distance d between the inner surface of hollow cathode 11 outer surface lower end and described anode 5
2it is 10 millimeters; The sidewall 13 of described anode 5 and the inner surface of diapire 9 form 135 ° of angles; Hollow cathode 11 inner diameter is 8 millimeters, and wall thickness is 1 millimeter; Reaction tube diameter is 14 millimeters, and wall thickness is 2 millimeters; Length is 30 millimeters.The wall of described reaction tube 14 is made up of copper near top, and other regions are made up of steel, utilizes the water of the anchor ring gap high speed circulation between described wall and its protection overcoat to cool the wall of described reaction tube 14 simultaneously.
A kind of high volatile bituminous coal is worn into pulverized coal particle, and its domain size distribution (PSD) is: 72 % by weight < 106 microns, 100 % by weight < 150 microns.As pan feeding, be introduced in described chamber together with the argon hydrogen mixture carrier gas that 300K coal dust is 2: 8 through hollow channel and the volume ratio of hollow cathode 11, same volume ratio be 2: 8 argon hydrogen mixture working gas be also introduced in above-mentioned chamber through its entrance, and be in plasma, in above-mentioned chamber, carbonaceous material and the region that plasmarized working gas is closing on arc column are rapidly mixed.
Through Industrial Analysis, calculate with dry ash free basis, coal dust, containing the volatile matter of about 40 % by weight, calculates with dry base (at 110 DEG C dry 2 hours) simultaneously, and coal dust has the element composition below shown in table 1:
Table 1
| Cw％ | Hw％ | Ow％ | Nw％ | Sw％ | H 2Ow％ | Ash content w% |
| 79.2 | 5.5 | 6.3 | 1.6 | 1.1 | 2.3 | 4.0 |
Described reactor assembly is run: system pressure is 115kPa under following operating condition, the power output of electrode is 10kW, pulverized coal flow 600g/h, argon hydrogen mixture flow 84g/h, being wherein 80g/h as working gas flow, is 4g/h as carrier gas flux.Be about 3000K at the regional temperature near arc column after argon hydrogen mixture is in plasma as working gas, wherein the hot-cast socket factor reaches about 84%, and high-temperature plasma air-flow enters in reaction tube after efficiently mixing with coal and carrier gas.Water is injected in reaction tube through two shock chilling medium entrances near pyrolysis product outlet, so as moment Quench or freeze formed product stream.The total residence time of coal dust in reactor assembly is about 25 milliseconds.The energy efficiency of described reactor is about 80%, that is, input power 80% by product stream and cooling plasma reactor system wall water absorb, the heat loss wherein caused by reaction tube is about 0.8kW.
The output product stream that described reactor assembly is formed under the operating conditions described above has acetylene yield shown in following table 2 and energy consumption:
Table 2
| Acetylene/100g coal | SER |
| 20.3g | 9.5kWh/kg-C 2H 2 |
In above-mentioned table 2, the electric power that SER refers to transmit with electrode is benchmark always than can demand (grossSpecific Energy Requirement).
Comparative example 1
Except replacing plasma reactor system of the present invention with existing plasma reactor system, repeat the experimental procedure described by embodiment 1, wherein coal dust and carrier gas pan feeding inject from the top of reaction tube, the high-temperature plasma air-flow of equivalent is injected into reaction tube from the sidepiece near top, and structure and the size of reaction tube are in the same manner as in Example 1.
The performance of two dissimilar reactor assemblies is arranged in table 3 below.Can obviously find out from table 3 by comparing: the performance of plasma reactor system of the present invention is better than the performance of existing plasma reactor system greatly.
Table 3
In above-mentioned table 3, the implication of SER and identical in table 2, energy efficiency refer to compared with input power by product stream and cooling water the relative populations of heat absorbed.
Embodiment 2
Except replacing the reactor assembly shown in Fig. 1 with the reactor assembly shown in Fig. 3, repeat the experimental procedure described by embodiment 1, the input power of one of two hollow cathode of wherein said plasma reactor system and/or anode is 15kW, to form the electric arc producing plasma.As shown in Figure 3, the entrance of described reactor assembly primarily of the entrance of two hollow cathode 11 and 19, anode 5, working gas 4, reaction tube 14, shock chilling medium 8 and the outlet composition of the cold product 10 of Quench, the nearest horizontal range d wherein between one of two hollow cathode 11 and 19 outer surface and the inner surface of described anode 5
1and d
3be respectively 12 millimeters and 15 millimeters; Minimum distance d between one of two hollow cathode 11 and 19 outer surface lower end and the inner surface of described anode 5
2and d
4be respectively 8 millimeters and 12 millimeters; The sidewall 13 of described anode 5 and the inner surface of diapire 9 form 135 ° of angles; Hollow cathode 11 inner diameter is 8 millimeters.Wall thickness is 1 millimeter; Another hollow cathode 19 inner diameter is 2 millimeters.Wall thickness is 1 millimeter; Reaction tube 14 inner diameter is 14 millimeters, and wall thickness is 2 millimeters; Length is 30 millimeters.The wall of described reaction tube is made up of copper near top, and other regions are made up of steel, utilizes the water of the anchor ring gap high speed circulation between described wall and its protection overcoat to cool the wall of described reaction tube 14 simultaneously.
Coal dust used in embodiment 3 is used identical with embodiment 1, and is ground into domain size distribution (PSD) and is: 80 % by weight < 106 microns; With the fine powder of 100 % by weight < 120 microns.
Described reactor assembly is run: system pressure is 125kPa under following operating condition, hollow cathode 11 is used as work negative electrode, the power output of electrode is 15kW, pulverized coal flow 800g/h, volume ratio be 2: 8 argon hydrogen mixture flow be 105g/h, be wherein 20g/h as preheating gas 15 flow; Be 80g/h as working gas 4 flow; Be 5g/h as carrier gas flux.450 DEG C of preheating gas 15 enter in above-mentioned chamber from the hollow channel of hollow cathode 19, and shift to an earlier date preheating coal dust, 3300K is about at the regional temperature near arc column after argon hydrogen mixture is in plasma as working gas, coal dust and carrier gas enter in above-mentioned chamber from the anchor ring slit that two hollow cathode 11 and 19 is formed, wherein the hot-cast socket factor reaches about 86%, and high-temperature plasma air-flow enters in reaction tube after efficiently mixing with coal dust and carrier gas pan feeding and preheating gas.Water is injected in reaction tube through two shock chilling medium entrances near pyrolysis product outlet, so as moment Quench or freeze formed product stream.The total residence time of coal dust in reactor assembly is about 25 milliseconds.The energy efficiency of described reactor assembly is about 82%, that is, input power 82% by product stream and for the wall that cools plasma reactor system cooling water absorb, the heat loss wherein caused by reaction tube is about 1.0kW.
The output product stream that described reactor assembly is formed under the operating conditions described above has acetylene yield below shown in table 4 and energy consumption:
Table 4
| Acetylene/100kg coal | SER |
| 22.5kg | 9.1kWh/kg-C 2H 2 |
In above-mentioned table 4, the electric power that SER refers to transmit with electrode is benchmark always than can demand (grossSpecific Energy Requirement).
Comparative example 2
Except replacing the plasma reactor system of the present invention shown in Fig. 3 with existing plasma reactor system, repeat the experimental procedure described by embodiment 2, wherein coal dust and carrier gas pan feeding inject from the top of reaction tube after being preheated to 200 DEG C, the high-temperature plasma air-flow of equivalent is injected into reaction tube from the sidepiece near top, and structure and the size of reaction tube are in the same manner as in Example 2.
The performance of two dissimilar reactor assemblies is arranged in table 5 below.Can obviously find out from table 5 by comparing: the performance of plasma reactor system of the present invention is better than the performance of existing plasma reactor system greatly, even not bad than the performance of the plasma reactor system described in embodiment 1.
Table 5
In above-mentioned table 5, identical with table 4 of SER implication, energy efficiency refer to compared with input power by product stream and cooling water the relative populations of heat absorbed.
The term that this description is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary, those of ordinary skill in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (31)
1. there is a plasma pyrolysis carbonaceous material reactor assembly for hollow cathode, comprising:
The hollow cathode of cooled medium circulation cooling and the anode of cooled medium circulation cooling, form the chamber that produces plasma and/or electric arc between described hollow cathode and anode;
Working gas entrance between described hollow cathode outer surface and described anode inner surface, enters in above-mentioned chamber for making described working gas;
Carbonaceous material and carrier gas pan feeding entrance, be positioned at described hollow cathode one end in the cavity, hollow channel in described hollow cathode is used as the transfer passage of carbonaceous material and carrier gas pan feeding, and carbonaceous material and carrier gas pan feeding enter in above-mentioned chamber through above-mentioned transfer passage by carbonaceous material and carrier gas pan feeding entrance;
The reaction tube be connected with above-mentioned anode;
At least one is positioned at above-mentioned reaction tube bottom for Quench or the shock chilling medium entrance freezing product; Be positioned at bottom above-mentioned reaction tube with at least one or the Quench product of bottom and the outlet of gas,
Wherein, described working gas is through the electric arc forming region between described hollow cathode and anode, thus generation plasma gas, and the plasma gas produced is in the highest temperature region of above-mentioned chamber or contact fully with carrier gas pan feeding with the carbonaceous material entering above-mentioned chamber from negative electrode hollow channel near it and mix, and causes pyrolysis.
2. there is a plasma pyrolysis carbonaceous material reactor assembly for two hollow cathode, comprising:
Two hollow cathode of cooled medium circulation cooling and the anode of cooled medium circulation cooling, the chamber that one produces plasma and/or electric arc is formed between one of any and anode of described pair of hollow cathode, one of them hollow cathode is positioned at the hollow channel of another hollow cathode, forms anchor ring slit between two hollow cathodes;
Working gas entrance between described pair of hollow cathode outmost surface and described anode inner surface, enters in above-mentioned chamber for making described working gas;
Carbonaceous material and carrier gas pan feeding entrance, be positioned at described pair of hollow cathode one end in the cavity, the described anchor ring slit of described pair of hollow cathode or innermost hollow channel are used as the transfer passage of carbonaceous material and carrier gas pan feeding, and carbonaceous material and carrier gas pan feeding enter in above-mentioned chamber through above-mentioned transfer passage by carbonaceous material and carrier gas pan feeding entrance;
The reaction tube be connected with above-mentioned anode;
At least one is positioned at above-mentioned reaction tube bottom for Quench or the shock chilling medium entrance freezing product; Be positioned at bottom above-mentioned reaction tube with at least one or the Quench product of bottom and the outlet of gas,
Wherein, described working gas is through the electric arc forming region between one of described pair of hollow cathode and anode, thus generation plasma gas, and the plasma gas produced is in the highest temperature region of above-mentioned chamber or contact fully with carrier gas pan feeding with the carbonaceous material entering above-mentioned chamber from the anchor ring slit of two hollow cathode or innermost hollow channel near it and mix, and causes pyrolysis.
3. reactor assembly according to claim 2, the described anchor ring slit of wherein said pair of hollow cathode or innermost hollow channel are used as the transfer passage of the preheating gas of working gas or preheating carbonaceous material and carrier gas pan feeding, and their bottom is used as the entrance of the preheating gas of working gas or preheating carbonaceous material and carrier gas pan feeding.
4., according to one of any described reactor assembly of claim 1-3, the nearest horizontal range between wherein said hollow cathode outer surface and the inner surface of described anode is 1-400 millimeter; And the minimum distance between described hollow cathode outer surface lower end and the inner surface of described anode is 1-400 millimeter.
5. reactor assembly according to claim 4, the minimum distance between wherein said hollow cathode outer surface lower end and the inner surface of described anode is 1-15 millimeter further.
6., according to claim 1-3 and 5 one of any described reactor assemblies, the inner surface forming range of wherein said anode side walls and diapire is the angle of 90o-160o.
7. reactor assembly according to claim 6, the further forming range of inner surface of wherein said anode side walls and diapire is the angle of 105o-145o.
8., according to claim 1-3,5 and 7 one of any described reactor assemblies, at least part of region of wherein said hollow cathode outer surface and anode outer surface is cooled medium circulation cooling, has cooling medium entrance and cooling medium outlet near it.
9. reactor assembly according to claim 3, the temperature wherein entering the preheating gas in the described anchor ring slit of described pair of hollow cathode or innermost hollow channel is 100-1000 DEG C.
10. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, the lower end of described anchor ring slit or the lower end of innermost hollow channel of the lower end of wherein said hollow cathode, two hollow cathode are connected with logistics distributor, in order to regulate flow velocity or the flow direction of carbonaceous material and carrier gas pan feeding, working gas and/or preheating gas.
11. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, the temperature of wherein said chamber highest temperature region guarantees that the temperature of the carbonaceous material entered wherein or in its vicinity reaches 650 DEG C ~ 1250 DEG C, and carbonaceous material temperature after entering described reaction tube reaches 1500 DEG C ~ 2900 DEG C.
12. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, wherein said working gas is becoming the high-temperature plasma gas of hydrogen, nitrogen, methane and/or inert gas after electric arc forming region.
13. reactor assemblies according to claim 3 or 9, wherein said preheating gas is the plasma gas of hydrogen, nitrogen, methane, inert gas and/or hydrogen, nitrogen, methane and/or inert gas.
14. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, the shock chilling medium wherein entered in described reaction tube guarantee product before leaving reaction tube by Quench to lower than 527 DEG C.
15. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, wherein the time of staying of carbonaceous material in described reaction tube is 0.4 ~ 4.0 millisecond.
16. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, in described reactor assembly, wherein there is carbonaceous material pyrolysis, the temporal summation of volatile matter gas-phase reaction and pyrolysis product Quench be less than 50 milliseconds.
17. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, wherein said shock chilling medium comprises water, propane, aromatic compound, inert gas and/or their mixture.
18. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, wherein said carrier gas is selected from hydrogen, nitrogen, methane, inert gas and/or their mixture.
19. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, the cross section of wherein said anode and/or reaction tube be circular, ellipse, polygon or any other regular shape.
20. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, the area ratio of wherein said reaction tube top and bottom cross section is 1/1-1/3.
21. according to claim 1-3,5,7 and 9 one of any described reactor assemblies, the entry number of wherein said carbonaceous material and carrier gas pan feeding is 1 ~ 32, and the entry number of described working gas is 2 ~ 32, and the entry number of described shock chilling medium is 2 ~ 64.
22. reactor assemblies according to claim 3 or 9, the entry number of wherein said preheating gas is 1 ~ 32.
23. reactor assemblies according to claim 21, wherein said various entrance is in the horizontal direction by symmetrical and/or relatively arrange.
24. according to claim 1-3,5,7,9 and 23 one of any described reactor assemblies, wherein said carbonaceous material is selected from coal, coal tar, coal directly-liquefied residue, heavy oil residue, Jiao, oil-sand, shale oil, living beings, synthetic plastic, Municipal solid rubbish, pitch and/or their mixture.
25. according to claim 1-3,5,7,9 and 23 one of any described reactor assemblies, the input power of wherein said hollow cathode and/or anode is 10kW ~ 20MW, to form the electric arc producing plasma gas.
26. according to claim 1-3,5,7,9 and 23 one of any described reactor assemblies, the entrance of wherein said working gas and/or the entrance of shock chilling medium are centrosymmetric distribution in the horizontal direction.
27. reactor assemblies according to claim 26, the entrance of wherein said shock chilling medium in the horizontal direction forming range is the angle of-45 ° to+45 °.
28. according to claim 1-3,5,7,9 and 23 one of any described reactor assemblies, wherein two in the horizontal direction relatively or the entrance of directly not relative described shock chilling medium vertically shape is at an angle.
29. according to claim 1-3,5,7,9 and 23 one of any described reactor assemblies, the volume ratio of wherein carbonaceous material and carrier gas is 10/90 ~ 90/10.
30. according to claim 1-3,5,7,9 and 23 one of any described reactor assemblies, wherein pyrolysis product comprises acetylene, carbon monoxide, methane, ethene and Jiao.
31. according to claim 1-3,5,7,9 and 23 one of any described reactor assemblies, wherein the average grain diameter of carbonaceous material is 10 ~ 300 microns.
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| CN103127895B (en) | 2011-12-01 | 2015-04-08 | 北京低碳清洁能源研究所 | Multi-section plasma cracking carbonaceous material reactor system with hollow cathode |
| CN103333043B (en) * | 2013-06-19 | 2015-02-04 | 浙江大学 | Method for preparing acetylene by cracking waste grease with thermal plasma |
| CN104788277B (en) * | 2014-01-22 | 2018-06-08 | 神华集团有限责任公司 | The method and apparatus for preparing acetylene |
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| CN110397929A (en) * | 2019-07-02 | 2019-11-01 | 苏州微木智能***有限公司 | A kind of plasma destroying system and destroying method |
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