CN102949972A

CN102949972A - Multi-stage plasma cracking carbonaceous material reactor and method for producing acetylene by using same

Info

Publication number: CN102949972A
Application number: CN2011102493298A
Authority: CN
Inventors: 程易; 郭屹; 颜彬航; 吴昌宁; 李轩
Original assignee: National Institute of Clean and Low Carbon Energy
Current assignee: China Energy Investment Corp Ltd; National Institute of Clean and Low Carbon Energy
Priority date: 2011-08-26
Filing date: 2011-08-26
Publication date: 2013-03-06
Anticipated expiration: 2031-08-26
Also published as: WO2013029457A1; CN102949972B

Abstract

The invention discloses a reactor for cracking carbonaceous materials by multi-stage plasma, which comprises: a first section of the reaction tube for mixing the carbonaceous material, the carrier gas and the first heating gas and pyrolyzing the carbonaceous material; the second section to the Nth section of the reaction tube are mainly used for enabling volatile components generated by pyrolysis to generate gas phase reaction, wherein N is an integer greater than or equal to 2; at least one inlet for carbonaceous material and carrier gas feed located at the top of the first section of the reactor tube; at least one inlet for a first heated gas located at a side of the first section of the reaction tube; at least one second to Nth heating gas inlet respectively positioned on the side surfaces of the second section to the Nth section of the reaction tube, wherein the second to the Nth heating gas are high-temperature plasma gas; at least one inlet for a quench medium for quenching or freezing reaction products; at least one outlet for quench product and gas at the bottom or lower portion of the last section of the reactor tube.

Description

Multistage plasma pyrolysis carbonaceous material reactor and produce the method for acetylene with it

Technical field

The present invention relates to a kind of carbonaceous material of volatile matter that contains for cracking with the high energy efficiency apparatus and method of production high yield pyrolysis product, particularly, the method that relates to a kind of multistage plasma pyrolysis carbonaceous material reactor and utilize this multistage plasma reactor cracking carbonaceous material, more particularly, also relate to a kind of method of utilizing this multistage plasma reactor to produce acetylene.

Background technology

Usually, carbonaceous material and other compositions, other suitable thermal source heating of being known by arcing device or those of ordinary skills together such as hydrogen are in order to make carbonaceous material cracking or pyrolysis.The result who decomposes 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, for example, is conducive to the formation of intermediate product acetylene when reaction zone temperature is higher than 1300K, and or compare with the decomposition of simultaneous acetylene during near 1300K, also be conducive to the formation of acetylene.

Generally speaking, when electric arc was used as thermal source, arc-through gas, such as hydrogen caused gas temperature to be increased to high temperature in the short time at the utmost point.The arc column temperature reaches 8000K～20000K usually.Temperature when gas leaves electric arc is usually about 2000K～5000K.With this understanding, gas molecule, may partly be dissociated into hydrogen atom or even H such as hydrogen molecule ⁺Perhaps H ^-, produce thus high-temperature plasma gas.

In case high-temperature plasma gas, leave electric arc such as plasma hydrogen, plasma gas atom or ion, for example hydrogen atom just have the tendency that is exceedingly fast that recombines into molecule, and if so, they will discharge a large amount of heat.Except the sensible heat of plasma gas, a part of great majority of above-mentioned heat are absorbed near the atom of plasma gas or ion or the particles of carbonaceous material that contacts with it by heat conduction, convection current and radiation, thereby cause particles of carbonaceous material by pyrolysis and/or cracking or decomposition, more particularly, cause particles of carbonaceous material to emit its volatile ingredient, i.e. devolatilization.

Known with determine be: different with the carbonaceous material type, the decomposition of carbonaceous material and the step of devolatilization and condition can great changes have taken place.Before this, because of do not know as how reasonably cost obtain the pyrolysis product of high yield such as the method for acetylene by solid carbonaceous material, so gaseous state and liquid carbon material are the pan feedings that people commonly use.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 instruction people make some specific cleavage product of coming from solid carbonaceous material, still may not be very clear such as the maximized for example technical process of the productive rate of acetylene and technique dynamics such as a kind of mode of high energy efficiency how.

In the prior art, be the improvement that the productive rate maximization that makes some pyrolysis product that comes from solid carbonaceous material is carried out equipment and process, people have done a lot of trials and experiment.

For example, US4358629 discloses a kind of method that solid carbonaceous material is translated into acetylene of decomposing.Specifically, these patent instruction people select the operating condition of low cost, high yield.In this patent, the heat of suggestion carbonaceous material and gas and the particular value of enthalpy combine with specific particle diameter and reaction time.Above-mentioned all instructions and suggestion help to produce acetylene with commercial competitive cost.

In fact, US4358629 has described a kind of arc reactor, and its direction that moves along solid carbonaceous material comprises four zones, i.e. solid carbonaceous material powder dispersion area, arc region, reaction zone and chill zone successively.Because described powder is in the time of staying of arc region extremely short and described powder temporary transient thermal inertia this moment, the temperature of described powder keeps certainly close to its temperature at entrance, and the gas of flowing through simultaneously reaches the high temperature of 8000K.The solid carbonaceous material powder only is heated the air-flow heating by heat conduction and convection current at reaction zone.Like this, all electric power are inputted by thin arc region, namely be enough to the large energy that described powder temperature is increased to more than the 1800K is caused the irrational excessive gathering of energy, and the heat that will too concentrate inevitably is exposed on the wall of reactor, thereby causes reactor wall overheated.Must account near the heat of removing the wall of reactor about half of whole electric power input result, the waste of having to of a large amount of valuable energy for the wall of guard reactor.In addition, the specific region high temperature occurs the design of reactor wall structure, the selection of wall material is consisted of greatly challenge, also makes the wall protection become a difficult problem.

" pyrolysis of coal in hydrogen and helium plasma " (Baumann, H., Bittner, D., Beiers, H.G., Klein, J.﹠amp; Juntgen, H, Fuel, 1988, Vol.67, pp 1120-1123, August) and " pyrolysis in hydrogen gas plasma of some gaseous states and liquid hydrocarbon " (Beiers, H.G., Baumann, H., Bittner, D., Klein, J.and Juntgen, H, Fuel, 1988, Vol.67, pp 1012-1016, July) a kind of equipment that is described to carry out coal or gaseous state and liquid hydrocarbon pyrolysis is disclosed, it comprises a plasma generator and a plasma reactor.In described equipment, plasma generator is created in the high temperature gas flow that the output mean temperature is 3300K, and this air-flow is subsequently from the top entrance is introduced in reaction tube as reactor.Dry pulverized coal or gaseous state and liquid hydrocarbon are injected into the reaction tube from its sidepiece entrance near the top entrance, and wherein cold coal dust is estimated fully to mix with above-mentioned hot plasma air-flow.Yet, because plasma flow high-speed downstream, therefore and form the strong obstacle that convection cell-powder mixes, so that the contact between coal dust and the plasma flow and heat transfer efficiency are weakened, and the performance of reactor had a negative impact, simultaneously this structure of reactor and pan feeding arrangement causes almost can't avoiding coking phenomenon, because coal dust or gaseous state and liquid hydrocarbon wash away the wall surface with the knock-on reaction device continuously.

CN1562922 discloses a kind of described reactor of above-mentioned article that is similar to, be sprayed on the reaction tube to prevent the argon gas of reaction tube coking but introduced, yet disclosed reactor does not still overcome above-mentioned all technological deficiencies in this patent documentation.

US4536603 discloses the method for a kind of coal and thermal current reaction production acetylene, the method may further comprise the steps successively: make fuel, oxygen and steam reaction under the controlled condition of temperature, thereby generate and mainly to comprise hydrogen, carbon monoxide and water vapour and a small amount of carbon dioxide is arranged, substantially do not have O, OH and an 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 approximately 150-300 feet per second.The logistics quantity of control particulate coal and hot gas is in order to form the pressure that is about 10-100pisa and be about 1800-3000 °F temperature at reaction zone.The mixture of coal and hot gas is maintained under the above-mentioned pressure and temperature approximately 2-30 millisecond, thereby generates the product stream that comprises burnt and acetylene.The temperature of product stream is brought down below approximately 900 °F being less than in time of 2 milliseconds subsequently, so that the further reaction of basic termination, and from wherein reclaiming acetylene.Reclaim burnt and used as at least a portion of the fuel that produces hot gas.

US 4588850 discloses a kind of method of being produced acetylene and synthetic or reducing gas by coal with electric arc or plasma method, and the coal that wherein powders is 1-5kWh/Nm in a kind of energy density ³, the time of staying be 0.5-10 millisecond, temperature at least 1500 ℃ the arc reactor by pyrolysis,, be no more than like this 1.8 times of quantity of so-called volatile matter in the coal by the quantity of the derivative gaseous compound of coal.Remaining Jiao is fed in the second arc reactor after Quench subsequently, wherein by means of gasifying medium and in conjunction with electric arc or plasma method heating, Jiao is converted into synthetic or reducing gas therein, and Jiao is the 1-15 millisecond time of staying in reactor, and burnt temperature is at least 800 ℃.Air-flow from pyrolysis zone is cleaned, and with selective solution from wherein reclaiming acetylene.Gas after the process purifying step is cooled equally and purifies.

CN101742808 discloses a kind of high-power V shape plasma generator that can replace 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 gases, for example plasma hydrogen and inert gas.

US4367363 discloses and a kind ofly has been converted in the gaseous state output gas flow that produces the method for acetylene the method that reclaims pure acetylene from coal.Described gaseous state output gas flow passed through HCN and H in the acid gas removal stage ₂S is adsorbed on organic solvent, as in the 1-METHYLPYRROLIDONE, and with causticity reagent, wash to remove CO such as NaOH ₂And by preliminary treatment.In second stage, wash described gaseous state output gas flow with organic solvent, thereby the processing of processed gas is provided and separates pure acetylene product.In the phase III, the gas that the process second stage is processed is desulfurized subsequently with methanation and processes at first by hydrogenation.The output gas flow of processing through the phase III is recycled in the process that coal is converted into acetylene.In the quadravalence section, be purified and be recycled in phase I and/or the second stage from the organic solvent of second stage.

The disclosure of all above-mentioned lists of references is introduced with for referencial use in full at this.

In above-mentioned introduction to prior art and describing, to those skilled in the art, clearly there are a lot of defectives of being badly in need of solution in the single hop reactor for cracking or decomposition carbonaceous material.For example, when according to pyrolysis product, increase or when optimizing the reaction time of carbonaceous material powder, the height of single hop reactor can't arbitrarily lengthen such as the desired reaction temperature needs of the maximum yield of acetylene.Hot stream temperature descends rapidly along single hop reactor longitudinal direction, cause for the productive rate maximization reaction gas flow that makes pyrolysis product must be by Quench in shorter displacement, and therefore so that carbonaceous material to become the conversion of pyrolysis product very limited.Simultaneously as previously mentioned, serious energy waste and near reactor wall too high Temperature Distribution also be not allow unheeded serious technical problem.

The following describes to have represented and be specifically related to thermal decomposition and contain the solid carbonaceous material of volatile matter so that some is from the maximized reactor of productive rate of the specific cleavage product of solid carbonaceous material and the new understanding of method.Simultaneously, further provide as quickly as possible the heat solid particles of carbonaceous material decomposing as quickly as possible the described particle that discharges volatile matter, thereby avoided those volatile matter generation secondary responses in the solid carbonaceous particle and form burnt necessary technological parameter.

On the basis of above-mentioned analysis, by countless trials and experiment, the inventor has finally invented and has almost solved above-mentioned all defect, for example obtained being used for cracking or decomposing the new equipment of solid carbonaceous material of good contact efficient between carbonaceous material fine powder and the plasma flow, i.e. the greatly different multistage plasma reactor of fluid-powder hybrid concept in working mechanism and the existing single hop plasma reactor.

Summary of the invention

First aspect present invention provides a kind of multistage plasma pyrolysis carbonaceous material reactor, comprising: the reaction tube first paragraph is mainly used in making carbonaceous material, carrier gas and the first heated air to mix and the RESEARCH OF PYROCARBON material;

Reaction tube second segment～N section, the volatile matter generation gas-phase reaction that is mainly used in making pyrolysis to produce, wherein N is the integer more than or equal to 2;

At least one is positioned at the carbonaceous material at reaction tube first paragraph top and the entrance of carrier gas pan feeding;

At least one is positioned at the entrance of the first heated air of reaction tube first paragraph side;

At least one lays respectively at the entrance of the second～the N heated air of reaction tube second segment～N section side, and wherein said the second～the N heated air is high-temperature plasma gas;

The entrance that at least one is used for Quench or freezes the shock chilling medium of product;

At least one is positioned at reaction tube final stage bottom or the Quench product of bottom and the outlet of gas;

Wherein, carbonaceous material flows downward from the top of reaction tube first paragraph, arrives at last bottom or the bottom of reaction tube final stage, finishes simultaneously pyrolysis, gas-phase reaction and Quench process.

In above-mentioned multistage plasma reactor, preferably, the operating temperature of described reaction tube first paragraph will guarantee to make the temperature that enters carbonaceous material wherein to reach 650 ℃～1250 ℃, and the operating temperature of described reaction tube second segment～N section will guarantee that the gas-phase reaction temperature that occurs therein reaches 1500 ℃～2900 ℃.Described the first heated air is preferably the plasma gas of hydrogen, nitrogen, methane, inert gas and/or hydrogen, nitrogen, methane and/or inert gas, and the second～the N heated air is preferably the high-temperature plasma gas of hydrogen, nitrogen, methane and/or inert gas.On the other hand, enter shock chilling medium in the described reactor should guarantee to make wherein product before leaving reactor preferably by below the Quench to 527 ℃.

Equally preferably: the gas-phase reaction time that the volatile matter that is produced by pyrolysis occurs in reaction tube second segment～N section is 0.4～4.0 millisecond, and the temporal summation of the pyrolysis that occurs in described reactor, gas-phase reaction and Quench is less than 50 milliseconds, for example the 30-40 millisecond.Generally speaking, described shock chilling medium can comprise the carbonaceous material of water, water vapour, propane, aromatic compound, inert gas, any type and/or their mixture, simultaneously described carrier gas can be selected from hydrogen, methane, nitrogen, gaseous carbon material, inert gas and/or their mixture, particularly, but described inert gas argon gas.

The cross section of described reaction tube can be circle, square, oval, polygon or any other regular shape, and more preferably, the cross-sectional area of described reaction tube second segment～N section is 1～3 times of cross-sectional area of reaction tube first paragraph.In addition, the entrance quantity of described carbonaceous material and carrier gas is preferably 1～100, and the entrance quantity of described the first～the N heated air is preferably 2～32, and the entrance quantity of described shock chilling medium is preferably 8～100.Particularly preferably, above-mentioned entrance is in the horizontal direction by symmetrical and/or relatively arrange.

Broadly say, that described carbonaceous material can be is solid-state, liquid state and/or gaseous material, particularly, described carbonaceous material can further be 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 refuse, pitch and/or their mixture.

Generally speaking, the plasma gas of described hydrogen, nitrogen, methane and/or inert gas and high-temperature plasma gas can be the plasma generator generation of 10kW～20MW by input power.

For obtaining better chill effect, the entrance of described the first～the N heated air and the entrance of shock chilling medium are preferably formed in the horizontal direction scope and are-45 °-+45 ° angle.Equally, for obtaining better mixed effect and most optimal retention time, two in the horizontal direction relatively or not directly the entrance of the first～the relative N heated air vertically be preferably formed an angle, more preferably, two in the horizontal direction relatively or not directly the angle that vertically forms of the entrance of the first relative heated air greater than two direct angles of vertically forming of the entrance of the second～the relative N heated air relatively or not in the horizontal direction.

To those skilled in the art, very clear two relatively or directly the angle that vertically forms of the entrance of the second～the relative N heated air can be not identical or different in the horizontal direction.

Second aspect present invention provides a kind of method of using aforementioned multistage plasma reactor cracking carbonaceous material, comprising:

A) carbonaceous material is introduced in the top of reaction tube first paragraph by means of carrier gas through the entrance of carbonaceous material and carrier gas pan feeding;

B) through the entrance of the first heated air the first heated air air-flow is introduced in the described reaction tube first paragraph, is wherein forced carbonaceous material and carrier gas to mix with the first heated air, and carbonaceous material subsequently under the heat effect of the first heated air air-flow by pyrolysis;

C) respectively the second～the N heated air is introduced in reaction tube second segment～N section through the entrance of the second～the N heated air, gas-phase reaction occurs in volatile matter therein that wherein produced by pyrolysis, randomly, carbonaceous material continues by pyrolysis under the heat effect of the second～the N heated air air-flow, thereby produces cracking and/or thermal decomposition product;

D) through the shock chilling medium entrance described shock chilling medium is introduced in the described reactor, so that Quench or freeze described cracking and/or thermal decomposition product;

E) through Quench product and gas vent the residue of the carbonaceous material of cracking and/or thermal decomposition product, gas and/or pyrolysis is discharged described reactor.

Third aspect present invention provides a kind of method of using aforementioned multistage plasma reactor to produce acetylene, comprising:

D) through the entrance of described shock chilling medium shock chilling medium is introduced in the described reactor, thus Quench or freeze described cracking and/or thermal decomposition product;

E) through the outlet of Quench product and gas with cracking and/or thermal decomposition product, gas, and/or the residue of the carbonaceous material of pyrolysis is discharged described reactor;

F) from cracking and/or thermal decomposition product and gas, isolate acetylene.

Above-mentioned according to the present invention second or the method for the third aspect in, cracking and/or thermal decomposition product generally include acetylene, carbon monoxide, methane, ethene and burnt etc.Simultaneously, for obtaining dispersion effect and the firing rate of carbonaceous material the best, the average grain diameter of carbonaceous material is preferably 10～300 microns, and carbonaceous material temperature before entering described reactor is preferably 20～300 ℃, and the volume ratio of carbonaceous material and carrier gas is preferably 10/90～90/10.

The operating pressure of described reactor generally can be negative pressure-malleation.Carbonaceous material heated speed in the reaction tube first paragraph is preferably greater than 104K/ second.Pyrolysis product after it generates preferably in 4 milliseconds by Quench or freeze.The temperature of described the second～the N heated air, flow, and/or kind can be identical or not identical.

Description of drawings

Fig. 1 is the representative schematic diagram of two sections plasma reactors of the present invention.

Fig. 2 is the representative schematic diagram of three sections plasma reactors of the present invention.

The specific embodiment

Be further explained in detail the present invention by the description below with reference to accompanying drawing, wherein parts corresponding or that be equal to or the feature shown in the accompanying drawing represents with identical reference numerals.

The reaction of the volatile matter that generally speaking, is discharged by RESEARCH OF PYROCARBON material, for example bituminous coal plays a part necessary and important in pyrolysis product production.Because carbonaceous material experience and the gas of high reaction activity, the reaction that is exceedingly fast of for example high-temperature plasma gas, and such reaction requires moment to be terminated, so that can't describe or calculate above-mentioned pyrolysis and reaction with common process.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, just can not there be the sufficient time to reach the heat power balance, but therefore just can not generate the formed cigarette ash of volatile matter secondary response by the carbonaceous material generation 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 that pyrolysis product forms, be productive rate.In fact, one of main purpose of the present invention be exactly make some specific cleavage products, such as the maximization of the productive rate of acetylene, therefore understand and determine that characteristic, mechanism and the operating condition of above-mentioned pyrolysis and reaction are to finish key of the present invention.

Countless tests and observation confirm: the pyrolysis temperature of carbonaceous material, particularly solid carbonaceous material is preferably 650 ℃～1250 ℃, for example 680-1100 ℃, more preferably 700 ℃～930 ℃, be particularly preferably 750 ℃～900 ℃, for example 850 ℃, and the gas-phase reaction temperature of the volatile matter that is obtained by carbonaceous material is preferably 1500 ℃～2900 ℃, more preferably 1500 ℃～2500 ℃, being particularly preferably 1500 ℃～2000 ℃, for example is 1750 ℃ or 1850 ℃.

Said temperature has determined preferred operations temperature in the reaction tube first paragraph and the preferred operations temperature in reaction tube second segment～N section, because the pyrolysis of carbonaceous material mainly occurs in the reaction tube first paragraph, the volatile matter that surpasses maximum growing amount 60% forms in the reaction tube first paragraph, and the gas-phase reaction of above-mentioned volatile matter then mainly occurs in reaction tube second segment～N section.

In order to obtain desirable fast as far as possible and as far as possible completely conversion, the above-mentioned gas-phase reaction time of described volatile matter preferably is less than 4 milliseconds, and for example 2 milliseconds, more preferably less than 1 millisecond, particularly preferably be less than 0.4 millisecond, for example be less than 0.3 or 0.2 millisecond.Such reaction time can guarantee to obtain the high yield of pyrolysis product.

Generally speaking, the feasible method of the productive rate of raising pyrolysis product, particularly acetylene has following several:

At first, elementary volatile matter and at high-temperature plasma gas, such as plasma hydrogen and/or comprise that reactivity in the inert gas of helium is high but the reaction height that is exceedingly fast between the plasma composition that the time-to-live is short is being controlled some specific cleavage product, such as the productive rate of acetylene.Therefore, if RESEARCH OF PYROCARBON material and discharge high concentration or a large amount of volatile matters extremely fast, the productive rate of pyrolysis product will be higher, this can distribute by the ultra-fine grain diameter of choose reasonable carbonaceous material, or consider that the oxygen in the volatile matter can be converted into carbon monoxide and consume acetylene, adopts carbonaceous material low-grade but that oxygen content is low to realize.

Secondly, select the optimum operation condition of RESEARCH OF PYROCARBON material, in order to obtain the volatile matter of maximum quantity.Therefore, suitable pyrolysis time, pressure and/or temperature are to make described volatile matter growing amount reach maximum key.

The 3rd, above-mentioned volatile matter is contacted with the plasma composition of as much as possible high reaction activity, so doing can increase reaction surface and improve reaction conversion ratio.

The 4th, the reaction temperature of volatile matter and high reaction activity plasma composition is another key factor that affects the pyrolysis product productive rate, generally speaking, the productive rate of pyrolysis product increases with the temperature raising of above-mentioned gas-phase reaction, but but too high reaction temperature can cause forming cigarette ash and the hydrogen of quantitation.

Those of ordinary skills can obviously find out from above analysis: the gas-phase reaction of the pyrolysis of carbonaceous material and elementary volatile matter and high reaction activity plasma composition all is the most important process that forms pyrolysis product.Yet, the optimal processing parameter of pyrolysis or operating condition are usually different from optimal processing parameter or the operating condition of above-mentioned gas-phase reaction, if the structural design of the single hop plasma reactor that in prior art, exists, be that the gentle phase reaction of pyrolysis occurs in the same space or zone, the technological parameter of pyrolysis and gas-phase reaction or operation bar just can't reach good balance and optimization.

For above-mentioned fatal shortcoming, the inventor proposes and has invented a kind of multistage plasma reactor of brand new by countless trials and experiment, the multistage plasma reactor of inventing makes above-mentioned pyrolysis and gas-phase reaction occur in different spaces or the zone dexterously, thereby makes the technological parameter of pyrolysis and gas-phase reaction or operating condition reach simultaneously optimum.

At length, shown in Fig. 1-2, described multistage plasma reactor comprises:

The reaction tube first paragraph is mainly used in making carbonaceous material, carrier gas to mix with the first heated air, and the RESEARCH OF PYROCARBON material; Reaction tube second segment～N section, the volatile matter generation gas-phase reaction that is mainly used in making pyrolysis to produce, wherein N is the integer more than or equal to 2;

The structural design of above-mentioned multistage plasma reactor so that the technological parameter of pyrolysis and gas-phase reaction and operating condition controlled independently of one another or select and can be optimized simultaneously be possible, in any case and this to be the structural design of existing single hop plasma reactor also be beyond one's reach.

In above-mentioned multistage plasma reactor, because pyrolysis temperature is significantly less than the gas-phase reaction temperature, so wherein mainly occuring, the operating temperature of the reaction tube first paragraph of pyrolysis can be lower than wherein the mainly operating temperature of the reaction tube second segment of the gas-phase reaction of the plasma composition of the elementary volatile matter of generation and high reaction activity～N section, therefore the first heated air that is used for pyrolysis can be hydrogen, nitrogen, methane, inert gas and/or hydrogen, nitrogen, methane, and/or the plasma gas of inert gas, and the second～the N heated air can be hydrogen, nitrogen, methane, and/or the high-temperature plasma gas of inert gas.

For the pyrolysis product that prevents from being obtained by gas-phase reaction, decompose or cigarette ash and the hydrogen that secondary response finally forms low value occur such as acetylene, the pyrolysis product that generates must moment before leaving described reactor by Quench.Generally speaking, pyrolysis product after it forms preferably 4 milliseconds, for example within 2 milliseconds by Quench to 650 ℃, preferred 600 ℃, particularly preferably below 527 ℃.Described shock chilling medium can preferably include the carbonaceous material of water, water vapour, propane, aromatic compound, inert gas, any type and/or their mixture.

The pressure of described reactor assembly can be negative pressure-malleation, 70～200KPa for example, preferred 100～150KPa, more preferably 110～140KPa.The length of reactor and pan feeding flow typically depend on the time of staying and the reaction time of pan feeding in each section of reaction tube.The temporal summation of the pyrolysis that more typically, occurs in described reactor, gas-phase reaction and Quench preferably is less than 50 milliseconds.

In order to obtain excellent transmission efficiency ultra-fine grain or finely disseminated carbonaceous material and/or to realize fully mixing or close contact of carbonaceous material and heated air, usually need to be used 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 for example is argon gas and/or helium.

The cross section of described reactor is any shape, for example circular, square, oval, polygon or any other regular shape.But in order to prevent that reaction tube surface from obvious coking occuring, the cross-sectional area of described reaction tube the second～the N section is preferably 1～3 times of cross-sectional area of reaction tube first paragraph.Such design has prevented that pan feeding or pyrolysis product from directly washing away above-mentioned inner surface, also form or building up burnt thereon.

Equally, in order in described reactor inner space, to distribute equably or to disperse pan feeding, heated air, pyrolysis product and/or shock chilling medium, preferably: the entrance quantity of carbonaceous material and carrier gas is 1～100, the entrance quantity of the first～the N heated air is 2～32, and the entrance quantity of shock chilling medium is 8～100, and more preferably: above-mentioned entrance is in the horizontal direction by symmetrical and relatively arrange.

That the carbonaceous material that uses in multistage plasma reactor of the present invention can be is solid-state, liquid state and/or gaseous material, and being preferably solid carbonaceous material, it for example 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 refuse, pitch and/or their mixture.

In multistage plasma reactor of the present invention, the high-temperature plasma gas of used hydrogen, nitrogen, methane and/or inert gas and/or plasma gas can be produced by the plasma generator that an input power is 10kW～20MW.The details relevant with above-mentioned plasma generator can be taken from or with reference to aforementioned reference, US4358629 for example, and CN1562922A or CN 101742808A, in order to save space, being described in detail in this and saving about plasma generator.

Because the time of the carbonaceous material pyrolysis that mainly occurs in the reaction tube first paragraph, generally the reactivity than contained in the elementary volatile matter that mainly occurs in reaction tube second segment～N section and the high-temperature plasma gas was high, but the time of the gas-phase reaction of the plasma composition that the time-to-live is short is long, so the time of staying of pan feeding in first paragraph is much larger than its time of staying in second segment～N section, in order to realize this arrangement, preferably: two in the horizontal direction relatively or not directly the entrance of the first～the relative N heated air vertically shape is at an angle, and two in the horizontal direction relatively or not directly the angle that vertically forms of the entrance of the first relative heated air greater than two direct angles of vertically forming of the entrance of the second～the relative N heated air relatively or not in the horizontal direction, certainly, two relatively or directly the angle that vertically forms of the entrance of the second～the relative N heated air can be not identical or different in the horizontal direction.

In order to obtain the best chill effect to pyrolysis product, particularly fresh acetylene, in order to make their productive rate reach maximum, equally preferably: the in the horizontal direction formation scope of entrance of the entrance of described the first～the N heated air and shock chilling medium is-45 ° to+45 ° angle.

The above-mentioned novel structure design of multistage plasma reactor of the present invention has the following advantages and feature:

At first, when need to be according to pyrolysis product, when increasing or optimizing the stop of carbonaceous material powder or reaction time such as the desired reaction temperature of the maximum yield of acetylene, the height of multistage plasma reactor can arbitrarily be lengthened out.

Secondly, hot stream temperature along multistage plasma reactor longitudinal direction slowly or lax descend or even improve slightly the productive rate maximization reaction gas flow that will cause for making pyrolysis product can be by Quench in long displacement, this will improve the conversion ratio that carbonaceous material becomes pyrolysis product greatly.

The 3rd because adopt piecemeal or step heating, avoided serious energy waste and near reactor wall too high Temperature Distribution, the result, the concentrations that heat discharges can not occur.

Multistage plasma reactor of the present invention can be used to produce the pyrolysis product from various carbonaceous materials, and typical method is as described below:

A) carbonaceous material is incorporated in the top of reaction tube first paragraph by means of carrier gas through the entrance of described carbonaceous material and carrier gas pan feeding;

C) respectively the second～the N heated air is introduced in reaction tube second segment～N section through the entrance of the second～the N heated air, wherein gas-phase reaction occurs in the volatile matter of pyrolysis generation therein, randomly, carbonaceous material continues by pyrolysis under the heat effect of the second～the N heated air air-flow, thereby produces cracking and/or thermal decomposition product;

D) through the entrance of described shock chilling medium shock chilling medium is introduced in the described reactor, so that Quench or freeze described cracking and/or thermal decomposition product;

E) through the outlet of Quench product and gas with cracking and/or thermal decomposition product, gas, and/or the carbonaceous material residue of pyrolysis is discharged described reactor.

Generally speaking, the pyrolysis product of carbonaceous material is mixture, and it comprises acetylene, carbon monoxide, methane, ethene, hydrogen and burnt etc., if want to obtain some specific cleavage product, such as acetylene, just need to separate the mixture of described pyrolysis product, in order to obtain substantially pure pyrolysis product.For example, aforementioned reference US 4367363 discloses the separation method of isolating pure acetylene from above-mentioned cleavage product mixtures.In order to save space, to be described in detail in this and to save about what separate.

In order to obtain the optimum efficiency of carbonaceous material pyrolysis and cracking, except the structural design of multistage plasma reactor, also should further consider or select the physics and chemistry character of pan feeding, in order 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 is preferably 20～300 ℃.The volume ratio of carbonaceous material and carrier gas is generally 10/90～90/10, is preferably 20/80～80/20, and more preferably 30/70～70/30, be particularly preferably 40/60～60/40, for example 50/50.

At last, also should be clear: carbonaceous material heated speed in the reaction tube first paragraph be preferably greater than 10 ⁴K/ second, and for the flexibility that operates and under varying environment to the different demands of operation, the temperature of the second～the N heated air, flow, and/or kind can be identical or different.

Embodiment

Embodiment 1

The reactor that its schematic diagram is indicated on two sections coal plasma pyrolysis among Fig. 1 is used to coal is converted into acetylene and other chemicals.The plasma generator that described two sections plasma reactors are 10kW～20MW by means of an input power comes work.As shown in Figure 1, described reactor is by two sections straight cavities (being reaction tube), three top coal powder entrances, two the first heated air entrances, two the second heated air entrances, and two shock chilling medium entrances and a pyrolysis product outlet form.The wall of described reactor is made of copper near four heated air entrances, and other zones are made of steel, utilizes simultaneously at described wall and its and protects the water of the anchor ring gap high speed circulation between the overcoat to cool off the wall of described reactor.

A kind of high volatile volatile bituminous coal is worn into pulverized coal particle, particle diameter distribute (PSD) be: 72 % by weight＜106 micron, 100 % by weight＜150 micron.As pan feeding, 300 ° of K coal dusts are introduced in the top of reaction tube first paragraph with the hydrogen carrier gas through coal powder entrance.Through Industrial Analysis, calculate with dry ash free basis, coal dust contains the approximately volatile matter of 40 % by weight, calculates with dry basic (lower dry 2 hours at 110 ℃) simultaneously, and coal dust has the element shown in the following table 1 and forms:

Table 1

C w％	H w％	O w％	N w％	S w％	H ₂O w％	Ash content w%
							79.2	5.5	6.3	1.6	1.1	2.3	4.0

The described reactor of operation under following operating condition: system pressure is 115kPa, the input power of plasma generator is 60kW, pulverized coal flow 30kg/h, hydrogen flowing quantity 4.2kg/h (being 4.0kg/h as heating gas flow wherein, is 0.2kg/h as carrier gas flux).Hydrogen is heated to form the plasma hydrogen that temperature is about 2600K as heated air, in order to make hot conversion factor reach approximately 82%, plasma hydrogen is incorporated in reaction tube first paragraph and the second segment equably through two the first heated air entrances and two the second heated air entrances subsequently.Water is injected in the reactor near the shock chilling medium entrances the pyrolysis product outlet through two, so as moment Quench or freeze formed product stream.The total residence time of coal dust in reactor is about 40 milliseconds.The energy efficiency of described reactor is about 76%, that is to say, 76% of input power is absorbed by the water of the wall of product stream and cooling plasma generator and plasma reactor, and the heat loss that is wherein caused by reactor is about 4.8kW.

The output product stream of the described reactor that forms under the aforesaid operations condition has in acetylene yield and the energy consumption shown in the following table 2:

Table 2

Acetylene/100kg coal	SER
		19.0kg	10.5kWh/kg-C ₂H ₂

In above-mentioned table 2, SER refers to that the electric power that transmitted take electrode is total specific energy demand (gross Specific Energy Requirement) of benchmark.

The comparative example 1

Except replacing two sections plasma reactors with existing single hop plasma reactor, repeat embodiment 1 described experimental procedure, wherein two the second heated air entrances are deleted, and the heated air of equivalent is injected in the single hop of reaction tube through two the first heated air entrances.

The performance of two dissimilar reactors is arranged in the following table 3.By relatively can obviously finding out from table 3: except the coal conversion ratio was lower slightly, the performance of two sections plasma reactors of the present invention was better than the performance of existing single hop plasma reactor greatly.

Table 3

Embodiment	The comparative example 1	Embodiment 1
			Type of reactor	The single hop reactor	Two reactor
Acetylene yield, the kg/100kg coal	15.8	19.0
			SER，kWh/kg-C ₂H ₂	12.7	10.5
C in the product stream ₂H ₂Mass ratio, % by weight	26.2	31.7
			The coal conversion ratio, %	46.2	46.0
The heat flow loss of reactor wall, kW	5.5	4.8
			Energy efficiency, %	73.2	76.1

In above-mentioned table 3, identical in the implication of SER and the table 2, energy efficiency refers to compare with input power the relative populations of the heat of being absorbed by product stream and cooling water.

Embodiment 2

Repeat embodiment 1 described experimental procedure except replacing with three sections plasma reactors two sections plasma reactors, the plasma generator that wherein said three sections plasma reactors are 10kW～20MW by means of an input power comes work.As shown in Figure 2, described reactor is comprised of three sections straight cavities (being reaction tube), three top coal powder entrances, two the first heated air entrances, two the second heated air entrances, two the 3rd heated air entrances, two shock chilling medium entrances and a pyrolysis product outlet.The wall of described reactor is made of copper near six heated air entrances, and other zones are made of steel, and the water that is used in simultaneously the anchor ring gap high speed circulation between described wall and its protection overcoat cools off the wall of described reactor.Used identical among used coal dust and the embodiment 1 among the embodiment 2, and worn into particle diameter distribute (PSD) be: 80 % by weight＜106 micron; Fine powder with 100 % by weight＜120 micron.

The described reactor of operation under following operating condition: system pressure is 125kPa, the input power of plasma generator is 80kW, pulverized coal flow 40kg/h, hydrogen flowing quantity 5.25kg/h (being 5.0kg/h as heating gas flow wherein, is 0.25kg/h as carrier gas flux).Hydrogen is heated to form the plasma hydrogen that temperature is about 2800K as heated air, in order to make hot conversion factor reach approximately 84%, plasma hydrogen is subsequently in two the first heated air entrances, two the second heated air entrances and two the 3rd heated air entrances are incorporated into reaction tube first paragraph, second segment and the 3rd section equably.Water is injected in the reactor near the shock chilling medium entrances the pyrolysis product outlet through two, so as moment Quench or freeze formed product stream.The total residence time of coal dust in reactor is about 35 milliseconds.Estimated by Calculation of Heat Transfer and energy balance: the energy efficiency of described reactor is about 78.2%, that is to say, 78.2% of input power is absorbed by product stream and the cooling water that is used for the wall of cooling plasma generator and plasma reactor, and the heat loss that is wherein caused by reactor is about 5.0kW.

Acetylene yield and energy consumption shown in the table 4 below the output product stream of the described reactor that forms under the aforesaid operations condition has:

Table 4

Acetylene/100kg coal	SER
		19.5kg	10.3kWh/kg-C ₂H ₂

In above-mentioned table 4, SER refers to that the electric power that transmitted take electrode is total specific energy demand (gross Specific Energy Requirement) of benchmark.

The comparative example 2

Except replacing three sections plasma reactors with existing single hop plasma reactor, experimental procedure described in the repetition embodiment 2, wherein two the second heated air entrances and two the 3rd heated air entrances are deleted, and the heated air of equivalent is injected in the single hop of reaction tube by two the first heated air entrances.

The performance of two dissimilar reactors is arranged in the following table 5.By relatively from table 5, can obviously finding out: except the coal conversion ratio is lower slightly, the performance of three sections plasma reactors of the present invention is better than the performance of existing single hop plasma reactor greatly, even not worse than the performance of two sections plasma reactors described in the embodiment 1.

Table 5

Embodiment	The comparative example 2	Embodiment 2
			Type of reactor	The single hop reactor	Three sections reactors
Acetylene yield, the kg/100kg coal	15.5	19.5
			SER，kWh/kg-C ₂H ₂	12.9	10.3
C in the product stream ₂H ₂Mass ratio, % by weight	25.7	32.3
			The coal conversion ratio, %	47.3	47.2
The heat flow loss of reactor wall, kW	6.1	5.0
			Energy efficiency, %	74.5	78.2

In above-mentioned table 5, identical in SER implication and the table 4, energy efficiency refers to compare with input power the relative populations of the heat of being absorbed by product stream and cooling water.

The term that this specification is used and form of presentation only are used as descriptive and nonrestrictive term and form of presentation, the feature that will represent and describe unintentionally when using these terms and form of presentation or any equivalent exclusion of its part.

Although represented and described several embodiment of the present invention, the present invention is not restricted to described embodiment.On the contrary, those of ordinary skills should recognize that in the situation that do not break away from principle of the present invention and spirit can be carried out any accommodation and improvement to these embodiments, protection scope of the present invention is determined by appended claim and equivalent thereof.

Claims

1. multistage plasma pyrolysis carbonaceous material reactor comprises:

The reaction tube first paragraph is mainly used in making carbonaceous material, carrier gas and the first heated air to mix, and the RESEARCH OF PYROCARBON material;

2. multistage plasma reactor according to claim 1, the temperature that the operating temperature of wherein said reaction tube first paragraph guarantees to enter carbonaceous material wherein reaches 650 ℃～1250 ℃, and the operating temperature of described reaction tube second segment～N section guarantees that the gas-phase reaction temperature that occurs therein reaches 1500 ℃～2900 ℃ simultaneously.

3. multistage plasma reactor according to claim 1, wherein said the first heated air is the plasma gas of hydrogen, nitrogen, methane, inert gas and/or hydrogen, nitrogen, methane and/or inert gas, and the second～the N heated air is the high-temperature plasma gas of hydrogen, nitrogen, methane and/or inert gas simultaneously.

4. multistage plasma reactor according to claim 1, wherein enter shock chilling medium in the described reactor guarantee wherein product before leaving reactor by Quench to being lower than 527 ℃.

5. multistage plasma reactor according to claim 1, wherein gas-phase reaction time of occuring in reaction tube second segment～N section of the volatile matter that forms of pyrolysis is 0.4～4.0 millisecond.

6. multistage plasma reactor according to claim 1, the temporal summation of the pyrolysis that wherein occurs in described reactor, gas-phase reaction and Quench is less than 50 milliseconds.

7. multistage plasma reactor according to claim 1, wherein said shock chilling medium comprises the carbonaceous material of water, steam, propane, aromatic compound, inert gas, any type and/or their mixture.

8. multistage plasma reactor according to claim 1, wherein said carrier gas is selected from hydrogen, methane, nitrogen, gaseous carbon material, inert gas and/or their mixture.

9. according to aforementioned claim 3,7,8 each described multistage plasma reactors, wherein said inert gas is argon gas.

10. multistage plasma reactor according to claim 1, the cross section of wherein said reaction tube are circular, square, oval, polygon or any other regular shape.

11. multistage plasma reactor according to claim 1, the area of the second segment of wherein said reaction tube～N section cross section are 1～3 times of area of reaction tube first paragraph cross section.

12. multistage plasma reactor according to claim 1, the entrance quantity of wherein said carbonaceous material and carrier gas is 1～100, and the entrance quantity of described the first～the N heated air is 2～32, and the entrance quantity of described shock chilling medium is 8～100.

13. according to aforementioned claim 1-8 and each described multistage plasma reactor of 10-12, wherein said each entrance is in the horizontal direction by symmetrical and/or relatively arrange.

14. according to aforementioned claim 1-8 and each described multistage plasma reactor of 10-12, wherein said carbonaceous material is solid-state, liquid state and/or gaseous material.

15. according to aforementioned claim 1-8 and each described multistage plasma reactor of 10-12, wherein said carbonaceous material further 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 refuse, pitch and/or their mixture.

16. according to aforementioned claim 1-8 and each described multistage plasma reactor of 10-12, the plasma gas of wherein said high-temperature plasma gas and hydrogen, nitrogen, methane and/or inert gas is the plasma generator generation of 10kW～20MW by input power.

17. according to aforementioned claim 1-8 and each described multistage plasma reactor of 10-12, the in the horizontal direction formation scope of entrance of the entrance of wherein said the first～the N heated air and shock chilling medium is-45 ° to+45 ° angle.

18. according to aforementioned claim 1-8 and each described multistage plasma reactor of 10-12, wherein two in the horizontal direction relatively or not directly the entrance of the first～the relative N heated air vertically shape is at an angle.

19. multistage plasma reactor according to claim 18, wherein two in the horizontal direction relatively or not directly the angle that vertically forms of the entrance of the first relative heated air greater than two direct angles of vertically forming of the entrance of the second～the relative N heated air relatively or not in the horizontal direction.

20. according to aforementioned claim 1-8 and each described multistage plasma reactor of 10-12, wherein two in the horizontal direction relatively or not directly the angle that vertically forms of the entrance of the second～the relative N heated air be identical or different.

21. a use comprises according to the method for each described multistage plasma reactor cracking carbonaceous material among the aforementioned claim 1-20:

A) carbonaceous material is incorporated in the top of reaction tube first paragraph by means of carrier gas through the entrance of carbonaceous material and carrier gas pan feeding;

E) through the outlet of described Quench product and gas with cracking and/or thermal decomposition product, gas, and/or the carbonaceous material residue of pyrolysis is discharged described reactor.

22. the method that use is produced acetylene according to each described multistage plasma reactor among the aforementioned claim 1-20 comprises:

23. according to claim 21 or 22 described methods, wherein cracking and/or thermal decomposition product comprise acetylene, carbon monoxide, methane, ethene and Jiao.

24. according to claim 21 or 22 described methods, wherein the average grain diameter of carbonaceous material is 10～300 microns.

25. according to claim 21 or 22 described methods, wherein carbonaceous material temperature before entering described reactor is 20～300 ℃.

26. according to claim 21 or 22 described methods, wherein the volume ratio of carbonaceous material and carrier gas is 10/90～90/10.

27. according to claim 21 or 22 described methods, the operating pressure of wherein said reactor is that negative pressure is to malleation.

28. according to claim 21 or 22 described methods, wherein carbonaceous material in the reaction tube first paragraph heated speed greater than 10 ⁴K/ second.

29. according to claim 21 or 22 described methods, wherein pyrolysis product forms in rear 4 milliseconds by Quench at it.

30. according to claim 21 or 22 described methods, the temperature of wherein said the second～the N heated air, flow and/or kind are identical or different.