CN102949972B

CN102949972B - Multi-stage plasma cracking carbonaceous material reactor and method for producing acetylene by using same

Info

Publication number: CN102949972B
Application number: CN201110249329.8A
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: 2014-05-28
Anticipated expiration: 2031-08-26
Also published as: CN102949972A; WO2013029457A1

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 the method for producing acetylene with it

Technical field

The present invention relates to a kind of for cracking containing the carbonaceous material of volatile matter the high energy efficiency apparatus and method with production high yield pyrolysis product, particularly, relate to a kind of multistage plasma pyrolysis carbonaceous material reactor and utilize the method for 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

Conventionally, carbonaceous material and other compositions, heat as other suitable thermal source of being known by arcing device or those of ordinary skills 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 for example, reaction zone temperature is conducive to the formation of intermediate product acetylene during higher than 1300K, and or while approaching 1300K compared with the decomposition of simultaneous acetylene, be also conducive to the formation of acetylene.

Generally speaking,, in the time that electric arc is used as thermal source, arc-through gas, as hydrogen, causes gas temperature within the utmost point short time, to be increased to high temperature.Arc column temperature reaches 8000K～20000K conventionally.Temperature when gas leaves electric arc is conventionally in 2000K～5000K left and right.With this understanding, gas molecule, may partly be dissociated into hydrogen atom or even H as hydrogen molecule ⁺or H ^-, produce thus high-temperature plasma gas.

Once high-temperature plasma gas, as plasma hydrogen leaves electric arc, plasma gas atom or ion, for example hydrogen atom just have the tendency being exceedingly fast that recombines 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 are absorbed by the atom near 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 and definite: 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 if pyrolysis product that how reasonably cost obtains high yield by solid carbonaceous material is as the method for acetylene, so gaseous state and liquid carbon material are the conventional pan feedings of people.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, instruction people still may not be perfectly clear as a kind of mode of high energy efficiency how makes to come from some specific cleavage product of solid carbonaceous material, for example technical process as maximized in the productive rate of acetylene and technique dynamics.

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

For example, US4358629 discloses a kind of method of decomposing solid carbonaceous material and be translated into acetylene.Specifically, these patent instruction people select the operating condition of low cost, high yield.In this patent, suggestion 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 produce acetylene with commercial competitive cost.

In fact, US4358629 has described a kind of arc reactor, and its direction moving along solid carbonaceous material comprises four regions, i.e. solid carbonaceous material powder dispersion area, arc region, reaction zone and chill zone successively.Because the time of staying of described powder in arc region is extremely short and now temporary transient thermal inertia of described powder, the temperature of described powder keeps temperature at entrance close to it certainly, and the gas of simultaneously flowing through reaches the high temperature of 8000K.Solid carbonaceous material powder only heats by heat conduction and the heated air-flow of convection current at reaction zone.Like this, all electric power is inputted by thin arc region, the large energy that is enough to described powder temperature to be increased to more than 1800K causes the irrational excessive gathering of energy, and inevitably too concentrated heat is exposed on the wall of reactor, thereby causes reactor wall overheated.For the wall of guard reactor must account near the heat of removing the wall of reactor the half left and right of whole electric power input, result, a large amount of valuable energy have to waste.In addition, there is the design of high temperature to reactor wall structure, the greatly challenge of selection formation of wall material in specific region, also makes wall protection become a difficult problem.

" pyrolysis of coal in hydrogen and helium 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 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 output mean temperature is 3300K, and this air-flow is introduced in the reaction tube as reactor from top entrance subsequently.Dry pulverized coal or gaseous state and liquid hydrocarbon are from being injected into reaction tube near its sidepiece entrance of top entrance, 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 therefore form the strong obstacle that convection cell-powder mixes, so that the 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 and the wall surface of knock-on reaction device continuously.

CN1562922 discloses one and has been similar to the described reactor of above-mentioned article, be sprayed in reaction tube to prevent the argon gas of reaction tube coking but introduced, but disclosed reactor does not still overcome above-mentioned all technological deficiencies in this patent documentation.

US4536603 discloses a kind of coal and has reacted the method for producing acetylene with thermal current, the method comprises the following steps successively: under the controlled condition of temperature, make fuel, oxygen and steam reaction, mainly comprise hydrogen, carbon monoxide and water vapour and have a small amount of carbon dioxide, substantially there is no O, OH and an O thereby generate 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 logistics quantity of particulate coal and hot gas, to form and be about the pressure of 10-100pisa and be about the temperature of 1800-3000 °F at reaction zone.The mixture of coal and hot gas is maintained at about 2-30 millisecond under above-mentioned pressure and temperature, thereby generates the product stream that comprises burnt and acetylene.The temperature of product stream is brought down below approximately 900 °F within the time that is less than 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 fuel that produces hot gas.

US 4588850 discloses a kind of method of being produced acetylene and synthetic or reducing gas by coal by electric arc or plasma method, and the coal wherein powdering is 1-5kWh/Nm in a kind of energy density ³, the time of staying be in 0.5-10 millisecond, the temperature arc reactor that is at least 1500 ℃ by pyrolysis,, the quantity of the gaseous compound being derived by coal is like this no more than 1.8 times of 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 synthetic or reducing gas therein, and Jiao is 1-15 millisecond the 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 purifying step is cooled equally and purifies.

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, for example plasma hydrogen and inert gas.

US4367363 discloses and has a kind ofly been converted into from coal the method that reclaims pure acetylene in the gaseous state output gas flow producing the method for acetylene.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 1-METHYLPYRROLIDONE, and rinse to remove CO with causticity reagent, as NaOH ₂and by preliminary treatment.In second stage, rinse 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 of process second stage processing, first by hydrogenation, is desulfurized and methanation processing subsequently.The output gas flow of processing through the phase III is recycled in the process that coal is converted into acetylene.In fourth stage, be purified and be recycled in first stage and/or 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 and description to prior art, to those skilled in the art, clearly there are a lot of defects of being badly in need of solution for the single hop reactor of cracking or decomposition carbonaceous material.For example, in the time need to increasing or optimize the reaction time of carbonaceous material powder according to pyrolysis product, reaction temperature as desired in the maximum yield of acetylene, the height of single hop reactor cannot arbitrarily lengthen.Hot stream temperature declines rapidly along single hop reactor longitudinal direction, and causing productive rate for making pyrolysis product to maximize reaction gas flow must be by Quench in shorter displacement, and it is very limited therefore to make carbonaceous material become the conversion of pyrolysis product.Simultaneously as previously mentioned, serious energy waste and near reactor wall too high Temperature Distribution be also not allow unheeded serious technical problem.

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

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

Summary of the invention

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

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

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～the N section side, and wherein said the second～the N heated air is high-temperature plasma gas;

At least one is for Quench or freeze the entrance of 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, finally arrives bottom or the bottom of reaction tube final stage, completes pyrolysis, gas-phase reaction and Quench process simultaneously.

In above-mentioned multistage plasma reactor, preferably, the temperature that the operating temperature of described reaction tube first paragraph will guarantee to make to enter carbonaceous material wherein reaches 650 ℃～1250 ℃, and the operating temperature of described reaction tube second segment～the N section will guarantee that the gas-phase reaction temperature occurring 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, entering shock chilling medium in described reactor should guarantee to make product wherein leaving before reactor preferably by below Quench to 527 ℃.

It is also preferred that: the gas-phase reaction time that the volatile matter being produced by pyrolysis occurs in reaction tube second segment～the N section is 0.4～4.0 millisecond, and the temporal summation of the pyrolysis, gas-phase reaction and the Quench that occur in described reactor is less than 50 milliseconds, for example 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, described carrier gas simultaneously 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～the 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 generator that, the plasma gas of described hydrogen, nitrogen, methane and/or inert gas and high-temperature plasma gas can be 10kW～20MW by input power produces.

For obtaining better chill effect, it is the angle of-45 °-+45 ° that described the first～the entrance of N heated air and the entrance of shock chilling medium are preferably formed scope in the horizontal direction.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 be vertically preferably formed an angle, more preferably, two angles that relatively or directly the entrance of the first relative heated air does not vertically form are in the horizontal direction greater than two in the horizontal direction relatively or the angle that directly the entrance of the second～the relative N heated air does not vertically form.

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

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

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

B) through the entrance of the first heated air, the first heated air air-flow is introduced in described reaction tube first paragraph, wherein force 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～the N section through the entrance of the second～the N heated air, there is therein gas-phase reaction in the volatile matter wherein being produced by pyrolysis, optionally, 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 shock chilling medium entrance, described shock chilling medium is introduced in 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 to described reactor.

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

D) through the entrance of described shock chilling medium, shock chilling medium is introduced in described reactor, thus 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 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 is preferably 20～300 ℃ entering temperature before described reactor, 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 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.

Accompanying drawing explanation

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

Fig. 2 is the representative schematic diagram of three sections of 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 or the identical reference numerals of feature corresponding or that be equal to shown in accompanying drawing represents.

The reaction of the volatile matter generally speaking, being discharged by RESEARCH OF PYROCARBON material, for example bituminous coal plays a part necessary and important in pyrolysis product is produced.Due to the gas of carbonaceous material experience and high reaction activity, for example high-temperature plasma gas be exceedingly fast react, and such reaction requires moment to be terminated, so that cannot or calculate above-mentioned pyrolysis and reaction with common process description.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 have the sufficient time to reach heat power balance, therefore just can not generate can quantitation the cigarette ash that forms of the volatile matter secondary response being produced by carbonaceous material.

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, i.e. productive rate.In fact, one of main purpose of the present invention be exactly make some specific cleavage products, as the productive rate of acetylene maximizes, characteristic, mechanism and the operating condition of therefore understanding and determine above-mentioned pyrolysis and reaction has been 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 being 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 the preferred operations temperature in preferred operations temperature and the reaction tube second segment～the N section in reaction tube first paragraph, because the pyrolysis of carbonaceous material mainly occurs in reaction tube first paragraph, the volatile matter that exceedes maximum growing amount 60% forms in reaction tube first paragraph, and the gas-phase reaction of above-mentioned volatile matter mainly occurs in reaction tube second segment～the N section.

In order to obtain desirable fast as far as possible and conversion as far as possible completely, the above-mentioned gas-phase reaction time of described volatile matter is preferably less than 4 milliseconds, and for example 2 milliseconds, more preferably less than 1 millisecond, be particularly preferably less than 0.4 millisecond, be for example 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:

First, elementary volatile matter and at high-temperature plasma gas, as plasma hydrogen and/or comprise that reactivity in the inert gas of helium is high but some specific cleavage product in the reaction height control being exceedingly fast between plasma composition that the time-to-live is short, as the productive rate of 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 can distribute by the ultra-fine grain diameter of choose reasonable carbonaceous material, or consider that the oxygen in 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, 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 many high reaction activities of trying one's best, so do and 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 pyrolysis product productive rate, generally speaking, the productive rate of pyrolysis product improves and increases with the temperature of above-mentioned gas-phase reaction, but too high reaction temperature can cause forming can quantitation cigarette ash and hydrogen.

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 is all the most important process that forms pyrolysis product.But, the optimal processing parameter of pyrolysis or operating condition are conventionally 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 existing in prior art, be that the gentle phase reaction of pyrolysis occurs in the same space or region, the technological parameter of pyrolysis and gas-phase reaction or operation bar just cannot reach good balance and optimization.

For above-mentioned fatal shortcoming, the inventor is proposed and has been 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 region dexterously, thereby makes the technological parameter of pyrolysis and gas-phase reaction or operating condition reach optimum simultaneously.

At length, as shown in Figure 1-2, described multistage plasma reactor comprises:

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

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

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

Decompose or secondary response occurs finally form cigarette ash and the hydrogen of low value for the pyrolysis product that prevents from being obtained by gas-phase reaction, as acetylene, the pyrolysis product generating leave before described reactor must moment by Quench.Generally speaking, pyrolysis product its form after preferably 4 milliseconds, for example within 2 milliseconds by Quench to 650 ℃, preferably 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, for example 70～200KPa, preferably 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 pyrolysis, gas-phase reaction and the Quench more typically, occurring in described reactor is preferably 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, conventionally 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 is for example argon gas and/or helium.

Any shape of the cross section of described reactor, for example circular, square, oval, polygon or any other regular shape.But in order to prevent that reaction tube surface from obvious coking occurring, 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 formation thereon or accumulation Jiao.

Equally, in order to distribute equably in described reactor inner space 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 using 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 is for example 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 plasma generator that the high-temperature plasma gas of hydrogen used, nitrogen, methane and/or inert gas and/or plasma gas can be 10kW～20MW by an input power produces.The details relevant to above-mentioned plasma generator can be taken from or with reference to aforementioned reference, for example US4358629, 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 mainly occurring in reaction tube first paragraph is generally high than reactivity contained in the elementary volatile matter mainly occurring in reaction tube second segment～the N section and high-temperature plasma gas, but the time of the gas-phase reaction of short plasma composition of time-to-live is long, so the time of staying of pan feeding in first paragraph be time of staying in second segment～the N section much larger than it, 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 angles that relatively or directly the entrance of the first relative heated air does not vertically form are in the horizontal direction greater than two in the horizontal direction relatively or the angle that directly the entrance of the second～the relative N heated air does not vertically form, certainly, two angles that directly entrance of the second～the relative N heated air vertically forms relatively or not in the horizontal direction can be identical or different.

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

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

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

Secondly, along multistage plasma reactor longitudinal direction slowly or lax decline or improve even slightly can be by Quench in longer displacement by causing productive rate for making pyrolysis product to maximize reaction gas flow, this will improve carbonaceous material and become the conversion ratio of pyrolysis product to hot stream temperature greatly.

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

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 through the entrance of described carbonaceous material and carrier gas pan feeding by means of carrier gas;

C) respectively the second～the N heated air is introduced in reaction tube second segment～the N section through the entrance of the second～the N heated air, there is therein gas-phase reaction in the volatile matter that wherein pyrolysis produces, optionally, 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 described reactor, 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 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, as acetylene, just need to separate the mixture of described pyrolysis product, 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 saving 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, 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 is preferably 20～300 ℃ entering temperature before described reactor.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.

Finally, also should be clear: carbonaceous material heated speed in reaction tube first paragraph is preferably greater than 10 ⁴k/ second, and for the flexibility that operates and under varying environment the different demands to 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 of coal plasma pyrolysis in Fig. 1 is used to coal to be converted into acetylene and other chemicals.The plasma generator that described two sections of plasma reactors are 10kW～20MW by means of an input power carrys out work.As shown in Figure 1, described reactor is by two sections of 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 up of copper near four heated air entrances, 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 carry out the wall of cooling described reactor simultaneously.

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

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

Under following operating condition, move described reactor: system pressure is 115kPa, the input power of plasma generator is 60kW, pulverized coal flow 30kg/h, hydrogen flowing quantity 4.2kg/h (being wherein 4.0kg/h as heating gas flow, is 0.2kg/h as carrier gas flux).Hydrogen is heated to form as heated air the plasma hydrogen that temperature is about 2600K, to make hot conversion factor reach approximately 82%, plasma hydrogen is incorporated in reaction tube first paragraph and second segment equably through two the first heated air entrances and two the second heated air entrances subsequently.Water is injected in reactor near shock chilling medium entrances 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 wherein being caused by reactor is about 4.8kW.

The output product stream of the described reactor forming under aforesaid operations condition has in acetylene yield and the energy consumption shown in 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 the electric power that transmitted take the electrode total specific energy demand (gross Specific Energy Requirement) as benchmark.

Comparative example 1

Except replacing two sections of plasma reactors with existing single hop plasma reactor, repeat the described experimental procedure of embodiment 1, 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 table 3 below.By relatively can obviously finding out from table 3: except coal conversion ratio is lower slightly, the performance of two sections of plasma reactors of the present invention is better than the performance of existing single hop plasma reactor greatly.

Table 3

Embodiment	Comparative example 1	Embodiment 1
			Type of reactor	Single hop reactor	Two reactor
Acetylene yield, kg/100kg coal	15.8	19.0
			SER，kWh/kg-C ₂H ₂	12.7	10.5
C in product stream ₂H ₂Mass ratio, % by weight	26.2	31.7
			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 with table 2 of the implication of SER, energy efficiency refers to compared with input power the hot relative populations by product stream and cooling water absorbed.

Embodiment 2

Except replacing two sections of plasma reactors with three sections of plasma reactors, repeat the described experimental procedure of embodiment 1, the plasma generator that wherein said three sections of plasma reactors are 10kW～20MW by means of an input power carrys out work.As shown in Figure 2, described reactor is made up of three sections of 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 up of copper near six heated air entrances, and other regions are made up of steel, and the water that is simultaneously used in the anchor ring gap high speed circulation between described wall and its protection overcoat carrys out the wall of cooling described reactor.In embodiment 2, coal dust used is used identical with embodiment 1, and be ground into particle diameter distribute (PSD) be: 80 106 microns of % by weight <; Fine powder with 120 microns of 100 % by weight <.

Under following operating condition, move described reactor: system pressure is 125kPa, the input power of plasma generator is 80kW, pulverized coal flow 40kg/h, hydrogen flowing quantity 5.25kg/h (being wherein 5.0kg/h as heating gas flow, is 0.25kg/h as carrier gas flux).Hydrogen is heated to form as heated air the plasma hydrogen that temperature is about 2800K, 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 reactor near shock chilling medium entrances 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 with for the cooling water of the wall of cooling plasma generator and plasma reactor, and the heat loss wherein being caused by reactor is about 5.0kW.

Acetylene yield and energy consumption shown in table 4 below the output product stream of the described reactor forming under 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 the electric power that transmitted take the electrode total specific energy demand (gross Specific Energy Requirement) as benchmark.

Comparative example 2

Except replacing three sections of plasma reactors with existing single hop plasma reactor, experimental procedure described in 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 table 5 below.By relatively can obviously finding out from table 5: except coal conversion ratio is lower slightly, the performance of three sections of plasma reactors of the present invention is better than the performance of existing single hop plasma reactor greatly, even not bad than the performance of two sections of plasma reactors described in embodiment 1.

Table 5

Embodiment	Comparative example 2	Embodiment 2
			Type of reactor	Single hop reactor	Three sections of reactors
Acetylene yield, kg/100kg coal	15.5	19.5
			SER，kWh/kg-C ₂H ₂	12.9	10.3
C in product stream ₂H ₂Mass ratio, % by weight	25.7	32.3
			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 with table 4 of SER implication, energy efficiency refers to compared with input power the hot relative populations by product stream and cooling water absorbed.

The term that this description is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, in the time using these terms and form of presentation, are not intended to any equivalent exclusion of the feature representing and describe or 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 in the situation that not departing from principle of the present invention and spirit can carry out any accommodation and improvement to these embodiments, and protection scope of the present invention is determined by appended claim and equivalent thereof.

Claims

1. a multistage plasma pyrolysis carbonaceous material reactor, comprising:

Reaction tube first paragraph, is mainly used in making carbonaceous material, carrier gas and the first heated air to mix, and 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～the N section guarantees that the gas-phase reaction temperature occurring 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 enters shock chilling medium in described reactor and guarantees that product is wherein leaving before reactor by Quench to lower than 527 ℃.

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

6. multistage plasma reactor according to claim 1, the temporal summation of the pyrolysis wherein occurring 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 steam, propane, aromatic compound, inert gas and/or their mixture.

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

9. according to aforementioned claim 3, the multistage plasma reactor described in 7,8 any one, wherein said inert gas is argon gas.

10. multistage plasma reactor according to claim 1, the cross section of wherein said reaction tube is circle, ellipse, polygon or any other regular shape.

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

12. multistage plasma reactors according to claim 1, the entrance quantity of wherein said carbonaceous material and carrier gas is 1～100, 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 the multistage plasma reactor described in aforementioned claim 1-8 and 10-12 any one, and wherein said each entrance is in the horizontal direction by symmetrical and/or relatively arrange.

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

15. according to the multistage plasma reactor described in aforementioned claim 1-8 and 10-12 any one, and wherein said carbonaceous material is further selected from coal, coal tar, coal directly-liquefied residue, heavy oil residue, Jiao, oil-sand, shale oil, carbonaceous industrial waste or tailing, living beings, synthetic polymer, municipal solid refuse and/or their mixture.

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

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

18. according to the multistage plasma reactor described in aforementioned claim 1-8 and 10-12 any one, 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 reactors according to claim 18, wherein two angles that relatively or directly the entrance of the first relative heated air does not vertically form are in the horizontal direction greater than two in the horizontal direction relatively or the angle that directly the entrance of the second～the relative N heated air does not vertically form.

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

21. 1 kinds of uses, according to the method for the multistage plasma reactor cracking carbonaceous material described in any one in aforementioned claim 1-20, comprising:

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

B) through the entrance of the first heated air, the first heated air air-flow is introduced in 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～the N section through the entrance of the second～the N heated air, there is therein gas-phase reaction in the volatile matter wherein being produced by pyrolysis, 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;

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

The method of acetylene is produced in 22. 1 kinds of uses according to the multistage plasma reactor described in any one in aforementioned claim 1-20, comprising:

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

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

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

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

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

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

29. according to the method described in claim 21 or 22, and wherein pyrolysis product forms in latter 4 milliseconds by Quench at it.

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