CN104785183A - Multi-section plasma cracking carbonaceous material reactor system - Google Patents

Multi-section plasma cracking carbonaceous material reactor system Download PDF

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CN104785183A
CN104785183A CN201510171978.9A CN201510171978A CN104785183A CN 104785183 A CN104785183 A CN 104785183A CN 201510171978 A CN201510171978 A CN 201510171978A CN 104785183 A CN104785183 A CN 104785183A
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carbonaceous material
plasma
gas
reaction
section
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CN104785183B (en
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李轩
苗强
韩建涛
黄峰
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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Shenhua Group Corp Ltd
National Institute of Clean and Low Carbon Energy
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/04—Thermal processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G15/00—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs
    • C10G15/12—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs with gases superheated in an electric arc, e.g. plasma
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Electromagnetism (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a multi-section plasma cracking carbonaceous material reactor system which includes a preheating section, at least one hybrid reaction section, at least one chilling medium inlet and at least one chilling product outlet, wherein the preheating section includes a hollow cathode and an anode; carbonaceous material enters a reaction tube of the preheating section through a hollow passage of the hollow cathode; the at least one hybrid reaction section includes a plurality of cathode bars and anodes corresponding to the cathode bars; a plasma and or/arc forming region formed between the hollow cathode and the anode is positioned inside the reaction tube, and a plasma and or/arc forming region formed among the cathode bars and the anodes is positioned outside the reaction tube; a plurality of streams of plasma gas collides at the center of or near to the reaction tube of the preheating section, and is in convection contact with and intensely mixed with carbonaceous material and carrier gas, so that preheated carbonaceous material is heated, carbonaceous material is subjected to pyrolysis and cracking, and then carbonaceous material subjected to pyrolysis and cracking is subjected to volatile matter gas-phase reaction. The reactor system provided by the invention is excellent in carbon deposition prevention and thermal efficiency and higher in split product productivity.

Description

A kind of multistage plasma pyrolysis carbonaceous material reactor assembly
Technical field
The present invention relates to a kind of for cracking containing the carbonaceous material of volatile matter with the high energy efficiency apparatus and method of production high yield pyrolysis product, particularly, relate to a kind of multistage plasma pyrolysis carbonaceous material reactor assembly and utilize the method for this multistage plasma reactor system cracking carbonaceous material, more particularly, a kind of method utilizing this multistage plasma reactor system to produce acetylene is related to.
Background technology
The product composition that carbonaceous material produces because of cracking or pyrolysis depends on reaction condition.As everyone knows, some specific reaction condition is conducive to the formation of some specific components, and such as, reaction zone temperature is higher than the formation being conducive to intermediate product acetylene during 1300K.
Generally speaking, when electric arc is used as thermal source, arc-through gas, as hydrogen, cause gas temperature in very short time to be increased to high degree, the temperature of arc column can reach 8000K ~ 20000K usually.When gas leaves electric arc, temperature is usually at about 2000K ~ 5000K.With this understanding, gas molecule, such as hydrogen molecule may become hydrogen atom or even H by partial dissociation +or H -, produce high-temperature plasma gas thus.
Once high-temperature plasma gas leaves electric arc, the atom of plasma gas or ion just have the tendency that is exceedingly fast recombining into molecule, and like this, they will discharge a large amount of heat.Except the sensible heat of plasma gas, above-mentioned heat most by heat conduction, convection current and radiation by near the atom of plasma gas or the particles of carbonaceous material of ion absorb, thus cause particles of carbonaceous material by pyrolysis and/or cracking, more particularly, particles of carbonaceous material is caused to release its volatile ingredient, i.e. devolatilization.
Known and determine: with the difference of carbonaceous material type, the cracking of carbonaceous material and the step of devolatilization and condition can great changes have taken place.Before this, because not knowing as how rational cost obtains the pyrolysis product of high yield as the method for acetylene, so gaseous state and liquid carbon material are the cracking pan feedings that people commonly use by Solid carbonaceous material.Gaseous state and liquid pan feeding are easy to process in addition, and lower to the loss of device of arc.
In the prior art, be the improvement that the maximize yield of some pyrolysis product coming from Solid carbonaceous material is carried out equipment and process, people have done a lot of trial and experiment.
US4358629 discloses a kind of arc reactor, and its direction along solid carbonaceous material movement comprises four regions successively, i.e. solid carbonaceous material powder dispersion district, arc region, reaction zone and chill zone.Because described powder is in the thermal inertia that the time of staying is extremely short and described powder is now temporary transient of arc region, the temperature of described powder keeps close to its temperature at entrance, and gas reaches the high temperature of 8000K, like this, powder only passes through heat conduction, radiation and convection current by gas-heated at reaction zone.Like this, all electric power is inputted by thin arc region, namely the large energy being enough to described powder temperature to be increased to more than 1800K causes the irrational excessive gathering of energy, and inevitably by the beat exposure too concentrated on the wall of reactor, thus cause reactor wall overheated.About the wall of guard reactor and the heat that must remove near the wall of reactor accounts for the half of whole electric power input, result, a large amount of valuable energy is had to waste.In addition, specific region occurs that high temperature forms great challenge to the design of reactor wall structure, the selection of wall material, also makes wall protection become a difficult problem.
CN103127895A discloses a kind of multistage plasma pyrolysis carbonaceous material reactor assembly with hollow cathode, and every section of reactor assembly comprises hollow cathode and the hollow anode of the cooling of cooled medium circulation; Working gas entrance; Carbonaceous material and carrier gas pan feeding entrance; The reaction tube be connected with above-mentioned male or female, this external system also comprises the shock chilling medium entrance that at least one is positioned at last reaction tube bottom; The outlet of the Quench product bottom last reaction tube is positioned at at least one, wherein, the hollow cathode of first paragraph and be used as forming the chamber that produces plasma and/or electric arc between the hollow cathode of any a section of reaction tube and anode, plasma flow contacts with carbonaceous material fully with carrier gas pan feeding and/or volatiles and mixes near above-mentioned chamber highest temperature region or its, concurrent heat-dissipating solution and/or gas-phase reaction.In above-mentioned multistage plasma pyrolysis carbonaceous material reactor assembly, because the chamber forming a generation plasma and/or electric arc between every section of hollow cathode and hollow anode is all arranged in the reaction tube of each section, carbonaceous material and/or volatiles and plasma flow be equally also arranged in the above-mentioned chamber highest temperature region of each section of reaction tube or its near contact fully and mix, although substantially improve the thermal efficiency of reactor like this, but in each section of reaction tube carbonaceous material or pyrolysis product temperature too high, and react tube wall when there is no a suitable safeguard measure, this structure of reactor and pan feeding arrangement cause almost unavoidable coking phenomenon, because pyrocarbon material powder or gaseous breakdown products likely contact continuously or wash away the wall surface of reactor.
In above-mentioned existing plasma reactor, no matter how structure of reactor designs, improve the thermal efficiency and pyrolysis product productive rate and almost become an implacable contradiction with the coking of eliminative reaction wall surface, how to accomplish to improve the thermal efficiency and pyrolysis product productive rate and the coking of eliminative reaction wall surface is the difficult problem perplexing industry simultaneously.
By countless exploration and experiment, the present inventor has found the technical scheme of the above-mentioned difficult problem of solution finally, thus develops and can improve the thermal efficiency and pyrolysis product productive rate and the multistage plasma pyrolysis carbonaceous material reactor assembly of eliminative reaction wall surface coking and utilize the method for this multistage plasma reactor system cracking carbonaceous material simultaneously.
Summary of the invention
The invention provides a kind of multistage plasma pyrolysis carbonaceous material reactor assembly, system comprises:
A preheating section, comprising: the hollow cathode of cooled medium circulation cooling and anode; Working gas entrance between described hollow cathode or anode surface, enter by the plasma of above-mentioned hollow cathode and anodic formation and/or electric arc forming region for making described working gas, thus make described working gas become plasma, for preheating carbonaceous material and carrier gas pan feeding; Carbonaceous material and carrier gas pan feeding entrance, be positioned at one end of described hollow cathode, the hollow channel of described hollow cathode is used as the transfer passage of carbonaceous material and carrier gas pan feeding, and carbonaceous material and carrier gas pan feeding enter in the reaction tube of described preheating section through above-mentioned transfer passage by described carbonaceous material and carrier gas pan feeding entrance;
At least one hybrid reaction section, be positioned under described preheating section, the cathode bar comprising the cooling of multiple cooled medium circulation with a cathode bar described in multiple and the corresponding formation chamber housing of described cathode bar and the anode that cools of cooled medium circulation, is arranged in the chamber of described anodic formation by the plasma of described cathode bar and anodic formation and/or electric arc forming region; Working gas entrance between described cathode bar or anode surface, enter by the plasma of above-mentioned cathode bar and anodic formation and/or electric arc forming region for making described working gas, thus make described working gas become plasma, for heating carbonaceous material and the carrier gas pan feeding of preheating further, impel the carbonaceous material generation pyrolysis entered by the reaction tube of described preheating section in the reaction tube of described hybrid reaction section, cracking and volatile matter gas-phase reaction;
At least one shock chilling medium entrance, for Quench or freeze product, is positioned at hybrid reaction pars infrasegmentalis described in last; Outlet with at least one Quench product and gas, is positioned at described shock chilling medium entrance bottom,
Wherein, the plasma formed between the hollow cathode of preheating section and anode and/or electric arc forming region are arranged in the reaction tube of described preheating section, carbonaceous material the reaction tube of above-mentioned preheating section and carrier gas pan feeding is entered in described plasma and/or electric arc forming region or contact fully with the plasma gas produced and mix near it from described hollow cathode hollow channel, and carbonaceous material described in preheating and carrier gas pan feeding, cause the pyrolytic reaction of carbonaceous material; With
The plasma formed between the cathode bar of hybrid reaction section and anode and/or electric arc forming region are positioned at outside the reaction tube of described hybrid reaction section, the multiply plasma gas that multiply working gas enters described plasma and/or the generation of electric arc forming region through its entrance clashes near the reaction tube center of above-mentioned hybrid reaction section or its, and enter carbonaceous material in the reaction tube of above-mentioned hybrid reaction section and carrier gas pan feeding and its volatiles produced with the reaction tube by above-mentioned preheating section and carry out counter current contact and mix, the carbonaceous material of further heating preheating and carrier gas pan feeding, and impel described carbonaceous material generation pyrolysis, cracking and volatile matter gas-phase reaction.
Preferably, in above-mentioned reactor assembly, described multiple cathode bar and multiple anode corresponded are distributed in the surrounding of the reaction tube of described hybrid reaction section symmetrically, more preferably, described cathode bar is even number with the quantity of the anode corresponded, such as, described cathode bar is 4 with the quantity of the anode corresponded.
Usually, in above-mentioned reactor assembly, the minimum distance between the hollow cathode of described preheating section and anode surface is 1-400 millimeter.Described hollow cathode outer surface, cathode bar surface and at least part of region of anode interior are cooled medium circulation cooling, have cooling medium entrance and cooling medium outlet near it.
Preferably, in above-mentioned reactor assembly, the temperature of the plasma gas produced in described preheating section is guaranteed to make the temperature of the carbonaceous material entered in the reaction tube of preheating section reach 650 DEG C ~ 1250 DEG C; The temperature that the temperature of the multiply plasma gas produced in described hybrid reaction section guarantees to make to enter carbonaceous material in the reaction tube of hybrid reaction section or its volatiles reaches 1500 DEG C ~ 2900 DEG C.
Usually, in above-mentioned reactor assembly, described working gas is becoming the high-temperature plasma gas of hydrogen, nitrogen, methane and/or inert gas after described plasma and/or electric arc forming region; The shock chilling medium entered in the reaction tube of hybrid reaction pars infrasegmentalis described in last guarantee product before leaving reaction tube by Quench to lower than 527 DEG C.
Preferably, in above-mentioned reactor assembly, carbonaceous material and/or the time of staying of volatiles in described preheating section and each section of hybrid reaction section are 0.4 ~ 4.0 millisecond; In described reactor assembly, there is carbonaceous material pyrolysis, the temporal summation of cracking and volatile matter gas-phase reaction and pyrolysis product Quench is less than 50 milliseconds.
Usually, in above-mentioned reactor assembly, described shock chilling medium comprises: the carbonaceous material of aqueous water, water vapour, propane, aromatic compound, inert gas, any type and/or their mixture; Described carrier gas comprises: hydrogen, nitrogen, methane, gaseous carbon material, inert gas and/or their mixture; Described carbonaceous material is selected from coal, coal tar, coal directly-liquefied residue, heavy oil residue, Jiao, petroleum coke, oil-sand, shale oil, carbonaceous industrial waste or tailing, living beings, synthetic plastic, synthetic polymer, damaged tire, Municipal solid rubbish, pitch and/or their mixture.
Preferably, in above-mentioned reactor assembly, the input power of described hollow cathode, cathode bar and/or anode is 5kW ~ 20MW, to form the electric arc producing plasma gas; The volume ratio of described carbonaceous material and carrier gas is 10/90 ~ 90/10; Described pyrolysis product comprises acetylene, carbon monoxide, methane, ethene and Jiao; Average grain diameter for the described carbonaceous material of cracking is 10 ~ 300 microns.
Accompanying drawing explanation
Fig. 1 is the illustrative diagram of multistage plasma reactor system of the present invention.
Fig. 2 is the illustrative diagram of existing multistage plasma reactor system.
Fig. 3 is the illustrative diagram of the descending plasma reactor system of existing single hop closed-entry.
In FIG, each reference numerals represents following implication: 1-carbonaceous material and carrier gas; 2-preheating section working gas entrance; 3-preheating section hollow cathode circulating cooling water inlet; 4-preheating section hollow cathode circulating cooling water out; 5-preheating section anode circulation cooling water inlet; 6-preheating section anode circulation coolant outlet; 7,12-hybrid reaction section working gas entrance; 8,13-hybrid reaction section cathode bar circulating cooling water inlet; 9,14-hybrid reaction section cathode bar circulating cooling water out; 10,15-hybrid reaction section anode circulation cooling water inlet; 11,16-hybrid reaction section anode circulation coolant outlet; 17-shock chilling medium entrance; 18-product gas outlet; 21-preheating section hollow cathode; 22,23-hybrid reaction section cathode bar; 31-preheating section anode; 32,33-hybrid reaction section anode; 41-preheating section preheating mixed zone; 42-hybrid reaction section hybrid reaction district.
In fig. 2, each reference numerals represents following implication: 11,14 or 214-hollow cathode; 5,205 or 305-anode; 4,204 or 304-working gas entrance; 1-carbonaceous material and carrier gas pan feeding entrance; 14,214,314-reaction tube; 15,215-insulating element; 8-shock chilling medium entrance; 10-Quench product and gas vent; 20-electric arc forming region; 21-highest temperature region.
In figure 3, each reference numerals represents following implication: 1-carbonaceous material and carrier gas pan feeding entrance; 2-high-temperature plasma air flow inlet; 3-shock chilling medium entrance; 4-product gas outlet; 5-product gas.
Detailed description of the invention
Be further explained in detail the present invention by description below with reference to the accompanying drawings, the corresponding or equivalent parts wherein shown in accompanying drawing or the identical reference numerals of feature represent.
Generally speaking, the reaction of the volatile matter discharged by RESEARCH OF PYROCARBON material, such as bituminous coal plays an important role in pyrolysis product is produced.Due to carbonaceous material experience and the gas of high reaction activity, the reaction be exceedingly fast of such as high-temperature plasma gas, and such reaction requires to be terminated instantaneously, to such an extent as to cannot describe with common process or calculate above-mentioned pyrolysis and reaction.Broadly, pyrolysis product distribution depends on the type of carbonaceous material and the operating condition of employing, if reaction and/or the time of staying only have several milliseconds, the sufficient time just can not be had to reach thermodynamic equilibrium.
For solid carbonaceous material, the heat transfer of carbonaceous material and pyrolysis, homogeneous phase gas-solid reaction and homogeneous gas phase all can affect speed, the i.e. productive rate that pyrolysis product is formed.In fact, main purpose of the present invention also comprises makes some specific cleavage products, maximize yield as acetylene, therefore understands and determine that the characteristic of above-mentioned pyrolysis and reaction, mechanism and operating condition have been one of keys of the present invention.
Countless test confirms: the pyrolysis temperature of carbonaceous material, particularly solid carbonaceous material is preferably 650 DEG C ~ 1250 DEG C, such as 680-1100 DEG C, be more preferably 700 DEG C ~ 930 DEG C, be particularly preferably 750 DEG C ~ 900 DEG C, such as 850 DEG C, and the gas-phase reaction temperature of the volatile matter obtained by carbonaceous material is preferably 1500 DEG C ~ 2900 DEG C, is more preferably 1500 DEG C ~ 2500 DEG C, being particularly preferably 1500 DEG C ~ 2000 DEG C, such as, is 1750 DEG C or 1850 DEG C.
Said temperature determine carbonaceous material experience pyrolysis and discharge volatile matter preferable temperature and subsequently volatile matter carry out the preferable temperature of gas-phase reaction.In the present invention, formed in the region producing plasma and/or electric arc between the hollow cathode of carbonaceous material pyrolysis in described preheating section and anode and just start, and estimate that the volatile matter exceeding maximum growing amount 60% is formed in the reaction tube of above-mentioned preheating section, the gas-phase reaction of above-mentioned volatile matter is then main to be occurred in the reaction tube of hybrid reaction section.
Desirable fast as far as possible and transform as far as possible completely in order to obtain, the above-mentioned gas-phase reaction time of described volatile matter is preferably less than 4 milliseconds, such as 2 milliseconds, more preferably less than 1 millisecond, is particularly preferably less than 0.4 millisecond, such as, is less than 0.3 or 0.2 millisecond.Such reaction time can ensure the high yield obtaining pyrolysis product.
Generally speaking, the feasible method improving the productive rate of pyrolysis product, particularly acetylene has following several:
First, elementary volatile matter and at high-temperature plasma gas, as plasma hydrogen and/or comprise the high but reaction height be exceedingly fast between the plasma composition that the time-to-live is short of reactivity in the inert gas of helium and control some specific cleavage product, productive rate as acetylene.Therefore, if RESEARCH OF PYROCARBON material and discharge high concentration or a large amount of volatile matters extremely rapidly, the productive rate of pyrolysis product will be higher, this ultra-fine grain diameter by choose reasonable carbonaceous material distributes, or consider that the oxygen in volatile matter can be converted into carbon monoxide and consume acetylene, adopt the low-grade but carbonaceous material that oxygen content is low to realize.
Secondly, the optimum operation condition of RESEARCH OF PYROCARBON material is selected, to obtain the volatile matter of maximum quantity.Therefore, suitable pyrolysis time, pressure and/or temperature make described volatile matter growing amount reach maximum key.
3rd, above-mentioned volatile matter is contacted with the plasma composition of as far as possible many high reaction activities, so does and can increase reaction surface and improve reaction conversion ratio.
4th, the reaction temperature of volatile matter and high reaction activity plasma composition is another key factor affecting pyrolysis product productive rate, generally speaking, the productive rate of pyrolysis product improves with the temperature of above-mentioned gas-phase reaction and increases, but too high reaction temperature can cause being formed can the cigarette ash-Jiao of quantitation and hydrogen.
Those of ordinary skill in the art can obviously find out from above analysis: the pyrolysis of carbonaceous material and the gas-phase reaction of elementary volatile matter and high reaction activity plasma composition are all the most important processes forming pyrolysis product.But, the optimal processing parameter of pyrolysis or operating condition are usually different from the optimal processing parameter of above-mentioned gas-phase reaction or operating condition, if as the structural design of existing plasma reactor, i.e. the contacting and mixing of carbonaceous material and plasma flow, carbonaceous material pyrolysis, occur in the same space or region with volatile matter gas-phase reaction, not only because the region that carbonaceous material contacts with plasma flow and mix causes hot transfer efficiency to decline away from high-temperature region, and the technological parameter of pyrolysis and gas-phase reaction or operating condition also cannot reach well balance and optimization.If there is the high-temperature region of multiple formation high reaction activity plasma gas or electric arc in reaction tube simultaneously, the quantity that the volatile matter produced by carbonaceous material will be caused to carry out Jiao that secondary response is formed increases, these Jiao are attached on the wall of reactor, will have a strong impact on the work of reactor.Contradiction how between the thermal efficiency of concerted reaction device, product yield and the coking of eliminative reaction wall surface is a very difficult problem.
For above-mentioned technical barrier, the present inventor is proposed by countless exploration and experiment and has been invented a kind of multistage plasma reactor system of brand new, the multistage plasma reactor system invented makes above-mentioned pyrolysis and gas-phase reaction occur in different spaces or region dexterously, make the technological parameter of pyrolysis and gas-phase reaction or operating condition reach optimum simultaneously, a high-temperature region forming high reaction activity plasma gas or electric arc is only set simultaneously in the reaction tube of preheating section for preheating carbonaceous material and carrier gas pan feeding, thus avoid that reaction temperature in reactor is too high causes a large amount of coking in reactor wall surface, and ensure that the thermal efficiency that reactor assembly is higher.
Exemplarily property example, as shown in Figure 1, in multistage plasma reactor system of the present invention, the plasma formed between the hollow cathode 21 of preheating section and anode 31 and/or electric arc forming region are arranged in the reaction tube of described preheating section, carbonaceous material the reaction tube of above-mentioned preheating section and carrier gas pan feeding is entered in described plasma and/or electric arc forming region or contact fully with the plasma gas produced near it and mix herein from described hollow cathode 21 hollow channel, and carbonaceous material described in preheating and carrier gas pan feeding, cause the pyrolytic reaction of carbonaceous material.
Equally, as shown in Figure 1, in multistage plasma reactor system of the present invention, the cathode bar 22 of hybrid reaction section, 23 and anode 32, the plasma formed between 33 and/or electric arc forming region are positioned at outside the reaction tube of described hybrid reaction section, multiply working gas enters multiply plasma gas that described plasma and/or electric arc forming region produce in the reaction tube center of above-mentioned hybrid reaction section or near it, head-on collision occurs and enter carbonaceous material in the reaction tube of above-mentioned hybrid reaction section and carrier gas pan feeding and its volatiles produced with the reaction tube by above-mentioned preheating section carry out counter current contact and strongly mix through its entrance, the carbonaceous material of further heating preheating and carrier gas pan feeding, and impel described carbonaceous material generation pyrolysis, cracking and volatile matter gas-phase reaction.
The structural design of above-mentioned multistage plasma reactor system makes in the plasma of formed plasma flow between above-mentioned preheating section hollow cathode and anode and/or electric arc forming region, particularly in the highest temperature region of the contiguous arc column of described forming region or near to contact fully with carrier gas pan feeding with carbonaceous material and mix, pyrolysis is caused fast and while efficient heat transfer in realization, and discharge volatile matter, along with the lasting of heat transfer and carbonaceous material enter in the reaction tube of described hybrid reaction section, the further concurrent heating of the multiply plasma produced outward through the reaction tube of hybrid reaction section and strong convection current mixing, carbonaceous material and the volatile matter temperature formed promote further, and cause the gas-phase reaction of a large amount of volatile matter, thus produce various pyrolysis product, like this, the technological parameter of pyrolysis and gas-phase reaction and operating condition can be controlled independently of one another or be selected, also make them be optimised simultaneously and become possibility.
As shown in Figure 1, in preheating section, the forming region of plasma and/or electric arc and/or the position of highest temperature zone are by adjusting described hollow cathode 21, the position of anode 31, size and/or structural parameters and changing, such adjustment can guarantee carbonaceous material and carrier gas pan feeding 1 and/or volatiles and the preheated zone that plasma flow carries out fully contacting and efficiently mix be positioned at the highest temperature region of described plasma and/or electric arc forming region or its near, thus realize conducting heat fast and efficiently.Such as, the minimum distance between the surface of hollow cathode 21 and anode 31 is generally 1-400 millimeter, is preferably 1-15 millimeter, such as 10 millimeters.
In order to prevent hollow cathode 21, cathode bar 22,23 and/or anode 31,32,33 overheated, at least part of region of described hollow cathode 21 and cathode bar 22,23 outer surface and anode 31,32,33 is cooled medium circulation cooling, has cooling medium entrance 3,5,8 and 13 and cooling medium outlet 4,6,9 and 14 near it.
In above-mentioned multistage plasma reactor system, pyrolysis temperature is generally 650 DEG C ~ 1250 DEG C, gas-phase reaction temperature is then 1500 DEG C ~ 2900 DEG C, so pyrolysis temperature is significantly less than gas-phase reaction temperature, for promoting that the warm operation gas of pyrolysis is at the high-temperature plasma gas becoming hydrogen, nitrogen, methane and/or inert gas after plasma and/or electric arc forming region, through with the mixing and heat transfer of carbonaceous material and carrier pan feeding, carbonaceous material is preheated to 650 DEG C ~ 1250 DEG C.
In order to prevent from being obtained by gas-phase reaction pyrolysis product, as acetylene decomposition or cigarette ash-Jiao and the hydrogen that secondary response finally forms low value occurs, the pyrolysis product generated in the end a described hybrid reaction section reaction tube bottom must moment by Quench.Generally speaking, pyrolysis product after its formation preferred within 4 milliseconds, such as 2 millisecond by Quench to 650 DEG C, preferably 600 DEG C, particularly preferably less than 527 DEG C.Described shock chilling medium can preferably include aqueous water, water vapour, propane, aromatic compound, inert gas, the carbonaceous material of any type and/or their mixture.
The pressure of described reactor assembly can be negative pressure-malleation, such as 70 ~ 200KPa, preferably 100 ~ 150KPa, more preferably 110 ~ 140KPa.The length of reaction tube and pan feeding flow typically depend on the number of the time of staying of pan feeding in preheating section and hybrid reaction section, reaction time and hybrid reaction section.More typically, the temporal summation of the pyrolysis occurred in described reactor assembly, gas-phase reaction and Quench is preferably less than 50 milliseconds.
In order to obtain the excellent transmission efficiency of ultra-fine grain or finely disseminated carbonaceous material and/or realize fully mixing or close contact of carbonaceous material and plasma flow; usual needs are for transmitting the carrier gas of particles of carbonaceous material or fine powder, 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 argon gas and/or helium.
In order to prevent reactor wall surface from obvious coking occurring, in preheating section, the cross-sectional area of reaction tube is greater than the cross-sectional area of hollow cathode, and the cross-sectional area of preferred reaction pipe is 1 ~ 3 times of the cross-sectional area of hollow cathode.Such design prevents pan feeding or thermal decomposition product directly wash away the inner surface of above-mentioned reaction tube and are formed or build up burnt thereon.
Equally, in order to distribution or dispersed carbon material and carrier gas pan feeding, working gas (plasma gas), pyrolysis product and/or shock chilling medium equably in described reactor assembly inner space, preferably: the quantity of the entrance of carbonaceous material and carrier gas pan feeding, working gas (plasma gas), pyrolysis product and/or shock chilling medium can be multiple, and it is even more preferred that above-mentioned entrance in the horizontal direction can by symmetrical and relatively arrange.
The carbonaceous material used in plasma reactor system of the present invention can be solid-state, liquid and/or gaseous material, and be preferably solid carbonaceous material, such as, it is selected from coal, coal tar, coal directly-liquefied residue, heavy oil residue, Jiao, petroleum coke, oil-sand, shale oil, carbonaceous industrial waste or tailing, living beings, synthetic plastic, synthetic polymer, damaged tire, Municipal solid rubbish, pitch and/or their mixture.
In multistage plasma reactor system of the present invention, the input power of described hollow cathode 21, cathode bar 22,23 and anode 31,32,33 can be 1kW ~ 20MW, such as, be 5kW ~ 10MW, to form the electric arc producing plasma flow.The details relevant to plasma generator can be taken from or with reference to existing document, such as US4358629, CN1562922A or CN 101742808A, in order to save space, and being described in detail in this and saving about plasma generator.
Just start because carbonaceous material pyrolysis to enter at carbonaceous material in the plasma and/or electric arc forming region or the high-temperature region near it formed between above-mentioned preheating section hollow cathode 21 and preheating section anode 31, and in the reaction tube entering hybrid reaction section after still in continuation, so carbonaceous material pyrolysis time is usually high than the reactivity contained by the main elementary volatile matter that occurs in the reaction tube of hybrid reaction section and high-temperature plasma air-flow but the time that the is gas-phase reaction of the plasma composition that the time-to-live is short is long.
The novel structure of multistage plasma reactor system of the present invention has the following advantages and feature:
(1) in preheating section, due to carbonaceous material and carrier gas pan feeding and high-temperature plasma air flow contacts and the region that mixes close in preheating section reaction tube plasma and/or electric arc forming region highest temperature region or near, temperature and its of carbonaceous material are greatly improved in preheating section by the speed heated, while realizing quick and efficient heat transfer, carbonaceous material can discharge more volatile matters at short notice, this is conducive to forming more pyrolysis product in hybrid reaction section, simultaneously, the design that plasma and/or electric arc forming region and highest temperature zone thereof are arranged in preheating section reaction tube is also very beneficial for improving the thermal efficiency of reactor.
(2) be mainly preheated in preheating section due to carbonaceous material and pyrolysis occurs, the elementary volatile matter that its temperature is still not enough to pyrolysis is produced and reactivity high but carry out obvious gas-phase reaction between the plasma composition that the time-to-live is short, so, although it is higher to be arranged in the plasma of preheating section reaction tube and/or electric arc forming region and highest temperature zone temperature thereof, can not impels and reactor wall formed or builds up a large amount of Jiao.
(3) carbonaceous material pyrolysis just starts in preheating section reaction tube, and be continued until that it enters after in the reaction tube of hybrid reaction section, therefore, carbonaceous material contacts in preheating section reaction tube with high-temperature plasma air-flow, the time of mixing and pyrolysis is different with region from the time that elementary volatile matter gas-phase reaction mainly occurs in hybrid reaction section with region, this will make pyrolysis and gas-phase reaction occur in different spaces or region, thus the technological parameter of pyrolysis and gas-phase reaction or operating condition may be regulated and controled independently of one another, and reach optimum simultaneously, this becomes the conversion ratio of pyrolysis product by greatly improving carbonaceous material.
(4) in hybrid reaction section, multiply working gas is converted into multiply high-temperature plasma gas, these multiply high-temperature plasma gases carry amount of heat and enter after in the reaction tube of hybrid reaction section, in the reaction tube center of hybrid reaction section or near it, head-on collision occurs and enter carbonaceous material in the reaction tube of hybrid reaction section and carrier gas pan feeding and its volatiles produced with the reaction tube by preheating section carry out counter current contact and strongly mix, and rapid reaction temperature being brought up to impels carbonaceous material generation pyrolysis and cracking, the particularly temperature of the elementary volatile matter generation gas-phase reaction of pyrolysis generation, thus carbonaceous material is achieved and efficient between carrier gas pan feeding and high-temperature plasma air-flow, conduct heat fast and uniformly.This will greatly improve productive rate and the yield of pyrolysis product, particularly acetylene.
(5) although reaction temperature is higher in the reaction tube of hybrid reaction section, but it is different from preheating section, in hybrid reaction section, due to by the plasma produced between cathode bar and anode and/or electric arc forming region and highest temperature zone thereof not in the reaction tube of hybrid reaction section, and in the chamber formed by anode, the multiply high-temperature plasma air-flow produced carries amount of heat and leaves after multiple such chamber enters the reaction tube of hybrid reaction section, just carry out contacting and mixing with the volatiles of carbonaceous material and generation thereof, so both ensure that in the reaction tube of hybrid reaction section that there is sufficiently high reaction temperature, the excess calories of high-temperature plasma torch is prevented again to concentrate in the reaction tube of hybrid reaction section, the concentrations of Thermal release is caused to there will not be in reaction tube, thus avoid serious energy waste and near reactor wall, occur a large amount of coking and too high Temperature Distribution.
(6) in multistage plasma reactor system of the present invention, preheating section and the diverse structural design of hybrid reaction section make multistage plasma reactor system of the present invention solve the reactor assembly thermal efficiency, contradiction between cleavage reaction product yield and the coking of eliminative reaction wall surface well.
Multistage plasma reactor system of the present invention can be used to produce the pyrolysis product from various carbonaceous material, and typical method is as described below:
A) through the hollow channel of described hollow cathode, carbonaceous material is incorporated in preheating section reaction tube by means of carrier gas, is formed between the hollow cathode of preheating section and anode and be positioned at the generation plasma of preheating section reaction tube and/or the region of electric arc;
B) through the working gas entrance between hollow cathode or anode, working gas is incorporated in the region of above-mentioned generation plasma and/or electric arc, working gas is in plasma when passing through the electric arc forming region between hollow cathode and anode subsequently, and above-mentioned generation plasma and/or electric arc region or its highest temperature region or fully contact with carrier gas pan feeding with the carbonaceous material entered from hollow cathode hollow channel in above-mentioned preheating section reaction tube near it and mix, and cause pyrolytic reaction and/or a small amount of gas-phase reaction;
C) mixture of carbonaceous material and carrier gas pan feeding and/or volatiles and plasma flow enters in the reaction tube of hybrid reaction section subsequently, multiply working gas enters by the plasma produced between the cathode bar of hybrid reaction section and anode and/or electric arc forming region through its entrance, and be in plasma when passing through above-mentioned electric arc forming region, the multiply plasma gas produced carries amount of heat and enters after in the reaction tube of hybrid reaction section, in the reaction tube center of hybrid reaction section or near it, head-on collision occurs and enter carbonaceous material in the reaction tube of hybrid reaction section and carrier gas pan feeding and its volatiles produced with the reaction tube by preheating section carry out counter current contact and strongly mix, and rapid reaction temperature being brought up to impels carbonaceous material generation pyrolysis and cracking, the particularly temperature of the elementary volatile matter generation gas-phase reaction of pyrolysis generation, thus impel, in the reaction tube of hybrid reaction section, carbonaceous material cracking reaction occurs, particularly volatile matter gas-phase reaction, thus produce cracking and/or thermal decomposition product,
D) through described shock chilling medium entrance, shock chilling medium is incorporated into the bottom of last hybrid reaction section reaction tube, so that Quench or freeze described cracking and/or thermal decomposition product;
E) through Quench product and gas vent by cracking and/or thermal decomposition product, gas, and/or the carbonaceous material residue of pyrolysis discharges described reactor or reaction tube.
Generally speaking, the pyrolysis product of carbonaceous material is mixture, and it comprises acetylene, carbon monoxide, methane, ethene, hydrogen and Jiao etc., if want to obtain some specific cleavage product, as acetylene, just need the mixture being separated described pyrolysis product, to obtain substantially pure pyrolysis product.Such as, bibliography US4367363 discloses the separation method isolating pure acetylene from above-mentioned cleavage product mixtures.In order to save space, be described in detail in this save about what be separated.
In order to obtain the optimum efficiency of carbonaceous material pyrolysis and cracking, except the structural design of plasma reactor system, also should further consider or select the physics and chemistry character of pan feeding, to make the productive rate of pyrolysis product reach maximum.Generally speaking, the average grain diameter of carbonaceous material is preferably 10 ~ 300 microns, and carbonaceous material temperature before entering described reactor assembly is preferably 20 ~ 300 DEG C.The volume ratio of carbonaceous material and carrier gas is generally 10/90 ~ 90/10, is preferably 20/80 ~ 80/20, is more preferably 30/70 ~ 70/30, is particularly preferably 40/60 ~ 60/40, such as 50/50.
Finally, also should be clear: carbonaceous material and/or volatiles are preferably greater than 10 by the speed heated 4k/ second, and in order to the flexibility that operates with under various circumstances to the different demands of operation, described hollow cathode, cathode bar, anode and/or their position, size and/or structural parameters are adjustable.
Embodiment
Embodiment 1
Schematic diagram is that the reactor assembly of the multistage plasma pyrolysis carbonaceous material of the present invention of Fig. 1 is used to coal tar is converted into acetylene and other chemicals.Using the coal tar that produces in a kind of pyrolysis of coal process as carbonaceous material pan feeding, its character is as shown in table 1.
Table 1
In the invention described above multistage plasma reactor system, the hollow cathode 21 of preheating section and the input power of plasma torch thereof are 5kW, four cathode bars 22 and 23 of hybrid reaction section and the input power of plasma torch thereof are all 5kW, to form the arc region producing plasma and four arc region forming generation plasma in hybrid reaction section at preheating section.
As shown in Figure 1, the coal tar pan feeding 1 of 300K is introduced in described preheating section reaction tube under the conveying in argon carrier of the hollow channel of hollow cathode 21, volume ratio is that the argon hydrogen mixture working gas of 4:6 is introduced in through its entrance 2 in the arc region formed by hollow cathode 21 and anode 31 in preheating section reaction tube and is in plasma, wherein, coal tar pan feeding and plasmarized working gas close on arc column region 41 in preheating section arc region is rapidly mixed, thus rapidly by the preheating of coal tar pan feeding, and its temperature is risen to the temperature starting to carry out pyrolytic reaction.
Afterwards, coal tar pan feeding 1, the volatile matter that argon carrier and pyrolysis produce enters in the reaction tube of hybrid reaction section downwards, the argon hydrogen mixture working gas that four bursts of volume ratios are similarly 4:6 is introduced in four arc region that hybrid reaction section formed by cathode bar 22 and 23 and anode 32 and 33 through its entrance 7 and 12 and is in plasma, consequent four strands of high-temperature plasma air-flows enter the reaction tube center that is positioned at hybrid reaction section or near zone 42 clashes, and the coal tar pan feeding entered with the reaction tube by preheating section in the reaction tube of hybrid reaction section, carrier gas and volatiles carry out counter current contact and strong mixing, and rapid reaction temperature being brought up to impels coal tar that pyrolysis and cracking occur further, the temperature of the elementary volatile matter generation gas-phase reaction particularly making pyrolysis produce, thus form a large amount of cleavage reaction product, such as acetylene.
Cleavage reaction product, such as acetylene are entered the shock chilling medium Quench of the reaction tube bottom of hybrid reaction section or are freezed through its entrance 17, the outlet 18 finally by Quench product and gas is discharged reactor.
The invention described above multistage plasma reactor system runs under following operating condition: system pressure is 110kPa, the gross output of electrode is 25kW, coal tar flow 9kg/h, argon carrier flow is 125g/h, argon hydrogen mixture working gas flow 500g/h in preheating section, in hybrid reaction section, per share argon hydrogen mixture working gas flow is 200g/h.Coal tar is entered in the reaction tube of hybrid reaction section by after the plasma flow preheating of argon hydrogen mixture in the reaction tube of preheating section, and wherein, be about 3000K at the regional temperature near arc column, the hot-cast socket factor is more than 90%.
Coal tar, carrier gas and/or volatiles carry out fast with high-temperature plasma air-flow in the reaction tube of preheating section and hybrid reaction section, after efficient and Homogeneous phase mixing and heat transfer, produce a large amount of cleavage reaction products.Aqueous water is injected into the reaction tube bottom of hybrid reaction section as shock chilling medium through the shock chilling medium entrance 17 be positioned near pyrolysis product outlet 18, so as moment Quench or freeze formed cleavage reaction product stream, shock chilling medium-liquid velocity is 40kg/h.The total residence time of coal tar in reactor assembly is about 30 milliseconds.The energy efficiency of described reactor is about 80% through measuring and calculating, that is, input power 80% by reacting product stream and for the water that cools plasma reactor wall absorb, the heat loss wherein caused by reaction tube is about 4kW.
Comparative example 1
Schematic diagram is that the reactor assembly with three sections of plasma pyrolysis carbonaceous materials of hollow cathode of Fig. 2 is used to coal tar is converted into acetylene and other chemicals.Adopt with the identical coal tar used in embodiment 1 as carbonaceous material pan feeding.
The input power of the plasma torch of above-mentioned three sections of plasma reactor system first paragraph hollow cathodes and anodic formation is 5kW, the input power of the plasma torch of second segment and the 3rd section of hollow cathode and anodic formation is all 10kW, to form the electric arc producing plasma.As shown in Figure 2, described reactor assembly primarily of hollow cathode 11,14 and 214, anode 5,205 and 305, working gas entrance 4,204 and 304, be used as the reaction tube 14 of second segment hollow cathode and be used as reaction tube 214 and the 3rd section of reaction tube 314, the entrance of shock chilling medium 8 and the outlet composition of the cold product 10 of Quench of the 3rd section of hollow cathode, wherein, hollow cathode 11,14 and 214 outer surface and described anode 5, nearest horizontal range d between 205 and the inner surface of 305 1it is 12 millimeters; Hollow cathode 11,14 and 214 outer surface lower end and described anode 5, minimum distance d between 205 and the inner surface of 305 2be respectively 8 millimeters; The sidewall 13,213 and 313 of described anode 5,205 and 305 and the inner surface of diapire 9,209 and 309 form 135 ° of angles; First paragraph hollow cathode 11 inner diameter is 8 millimeters.Wall thickness is 1 millimeter; Reaction tube 14,214 and 314 inner diameter is 14 millimeters, and wall thickness is 2 millimeters; Length is 30 millimeters.The wall of described reaction tube 14,214 and 314 is made up of copper near top, and other regions are made up of steel, utilizes the water of the anchor ring gap high speed circulation between described wall and its protection overcoat to cool the wall of described reaction tube 14,214 and 314 simultaneously.Physical isolation is held with an insulating element 15,215 respectively between reaction tube 14,214 and anode 5,205.
Using coal tar used in the embodiment 1 carbonaceous material pan feeding as this comparative example 1, the coal tar of 300K is through hollow cathode 11, 14 with 214 hollow channel be introduced in described first paragraph together with argon carrier, in the chamber of second segment and the 3rd section, volume ratio is the argon hydrogen mixture working gas 4 of 4:6, 204 and 304 are also introduced in above-mentioned three chambers through its entrance, and be in plasma, in above-mentioned three chambers, coal tar and/or volatiles and plasmarized working gas are rapidly mixed in the region closing on arc column and are heated rapidly, and cause pyrolysis and the cracking reaction of coal tar, the particularly gas-phase reaction of volatiles.
Above-mentioned three sections of plasma reactor systems with hollow cathode are run: system pressure is 110kPa under following operating condition, the power output of first paragraph hollow cathode 11 and anode 5 is 5kW, the power output of second segment and the 3rd section of hollow cathode 14,214 and second segment and the 3rd section of anode 205,305 is all 10kW, coal tar flow 9kg/h, argon carrier flow is 125g/h, and the volume ratio being divided into the working gas 4,204 and 304 of impartial three parts is argon hydrogen mixture every part of flow of 4:6 is 430g/h.3000K is about at the regional temperature near arc column after argon hydrogen mixture is in plasma as working gas 4,204 and 304, coal tar and argon carrier pan feeding and/or volatiles enter above-mentioned three chambers from the hollow channel of three hollow cathodes 11,14 and 214, wherein, the hot-cast socket factor reaches about 86%, and high-temperature plasma air-flow enters in three reaction tubes 14,214 and 314 after efficiently mixing with coal tar and carrier gas pan feeding and/or volatiles.Water is injected in last reaction tube 314 through two shock chilling medium entrances 8 near pyrolysis product outlet 10, so as moment Quench or freeze formed reacting product stream.The total residence time of coal tar in reactor assembly is about 30 milliseconds.The energy efficiency of described reactor assembly is about 82%, that is, input power 82% by reacting product stream and for the water that cools plasma reactor wall absorb, the heat loss wherein caused by reaction tube is about 1.0kW.
Comparative example 2
Schematic diagram is that the reactor assembly of the descending plasma pyrolysis carbonaceous material of single hop closed-entry of Fig. 3 is used to coal tar is converted into acetylene and other chemicals.Adopt with the identical coal tar used in embodiment 1 as carbonaceous material pan feeding.
In the descending plasma reactor system of above-mentioned single hop closed-entry, producing the input power entering the plasma torch of the high-temperature plasma gas in reactor by its entrance 2 is 25kW, the argon hydrogen mixture of the working gas producing above-mentioned high-temperature plasma gas to be volume ratio be 4:6.
As shown in Figure 3, coal tar and argon carrier pan feeding 1 enter in reactor through the closed-entry passage of reactor head, wherein, coal tar and argon carrier pan feeding carry out rapid mixing and heat transfer in the reactor with the high-temperature plasma gas entered in reactor through its entrance 2, thus rapidly coal tar is heated, and its temperature is risen to cause Coal Tars reaction and cracking reaction temperature, particularly impel volatiles to carry out the temperature of gas-phase reaction, thus produce a large amount of cleavage reaction product, such as acetylene.
Cleavage reaction product, such as acetylene are entered the shock chilling medium Quench of reactor lower part through its entrance 3 or are freezed, and the outlet 4 finally by Quench product and gas is discharged reactor.
The descending plasma reactor system of above-mentioned single hop closed-entry runs under following operating condition: system pressure is 110kPa, the gross output of electrode is 25kW, coal tar flow 9kg/h, argon carrier flow is 125g/h, and the argon hydrogen mixture working gas flow for generation of above-mentioned high-temperature plasma gas is 1300g/h.Wherein, be about 3000K at the regional work gas temperature near arc column, the hot-cast socket factor is about 75%.
Coal tar, carrier gas and/or volatiles carry out rapid mixing with high-temperature plasma air-flow and after conducting heat, produce a large amount of cleavage reaction products in the descending plasma reactor of above-mentioned single hop closed-entry.Aqueous water is injected into reactor lower part as shock chilling medium through the shock chilling medium entrance 3 be positioned near pyrolysis product outlet 4, so as moment Quench or freeze formed cleavage reaction product stream 5, shock chilling medium-liquid velocity is 40kg/h.Coal tar total residence time is in the reactor about 30 milliseconds.The energy efficiency of described reactor is about 70% through measuring and calculating, that is, input power 70% by reacting product stream and for the water that cools plasma reactor wall absorb, the heat loss wherein caused by reaction tube is about 5kW.
The performance row of above-mentioned three dissimilar reactor assemblies in the following Table 2.
Table 2
Embodiment Embodiment 1 Comparative example 1 Comparative example 2
Reactor assembly type The present invention Three sections Single hop, reducing
Acetylene yield, g/1kg coal tar 413 453 193
Coking rate 181 418 163
Energy efficiency, % 80 82 70
SER,kWh/kg-C 2H 2 8.1 7.4 17.2
Methane production, g/kg coal tar 165 56 76.9
Carbon monoxide productive rate, g/kg coal tar 232 46 86.3
Carbon to gaseous product conversion ratio, % 76.46 58.25 31.68
C in product stream 2H 2Volume ratio, 38.21 55.89 28.17
Volume %
Coal tar conversion ratio, % 97 98 56
The heat flow loss of reactor wall, kW 4 1 5
In above-mentioned table 2, the electric power that SER refers to transmit with electrode is benchmark always than can demand (grossSpecific Energy Requirement); Carbon to gaseous product conversion ratio refers to the content ratio of carbon in carbon and coal tar in gaseous product; Energy efficiency refer to compared with input power by product stream and cooling water the relative populations of heat absorbed.
Experimental data from table 2: the reactor assembly (embodiment 1) of multistage plasma pyrolysis carbonaceous material of the present invention is compared with the reactor assembly (comparative example 2) of the existing reactor assembly (comparative example 1) and the descending plasma pyrolysis carbonaceous material of existing single hop closed-entry with three sections of plasma pyrolysis carbonaceous materials of hollow cathode, in the reactor assembly thermal efficiency (energy efficiency), good equilibrium is reached between cleavage reaction product (acetylene) yield and eliminative reaction wall surface coking (coking rate), overcome acetylene yield and energy efficiency in comparative example 1 completely high, but coking is serious and in comparative example 2 coking rate low, but the defect that acetylene yield and energy efficiency are not high.
The term that this description is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary, those of ordinary skill in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.

Claims (17)

1. a multistage plasma pyrolysis carbonaceous material reactor assembly, reactor assembly comprises:
A preheating section, comprising: the hollow cathode of cooled medium circulation cooling and anode; Working gas entrance between described hollow cathode or anode surface, enter by the plasma of above-mentioned hollow cathode and anodic formation and/or electric arc forming region for making described working gas, thus make described working gas become plasma, for preheating carbonaceous material and carrier gas pan feeding; Carbonaceous material and carrier gas pan feeding entrance, be positioned at one end of described hollow cathode, the hollow channel of described hollow cathode is used as the transfer passage of carbonaceous material and carrier gas pan feeding, and carbonaceous material and carrier gas pan feeding enter in the reaction tube of described preheating section through above-mentioned transfer passage by described carbonaceous material and carrier gas pan feeding entrance;
At least one hybrid reaction section, be positioned under described preheating section, the cathode bar comprising the cooling of multiple cooled medium circulation with a cathode bar described in multiple and the corresponding formation chamber housing of described cathode bar and the anode that cools of cooled medium circulation, is arranged in the chamber of described anodic formation by the plasma of described cathode bar and anodic formation and/or electric arc forming region; Working gas entrance between described cathode bar or anode surface, enter by the plasma of above-mentioned cathode bar and anodic formation and/or electric arc forming region for making described working gas, thus make described working gas become plasma, for heating carbonaceous material and the carrier gas pan feeding of preheating further, impel the carbonaceous material generation pyrolysis entered by the reaction tube of described preheating section in the reaction tube of described hybrid reaction section, cracking and volatile matter gas-phase reaction;
At least one shock chilling medium entrance, for Quench or freeze product, is positioned at hybrid reaction pars infrasegmentalis described in last; With
The outlet of at least one Quench product and gas, is positioned at described shock chilling medium entrance bottom,
Wherein, the plasma formed between the hollow cathode of preheating section and anode and/or electric arc forming region are arranged in the reaction tube of described preheating section, carbonaceous material the reaction tube of above-mentioned preheating section and carrier gas pan feeding is entered in described plasma and/or electric arc forming region or contact fully with the plasma gas produced and mix near it from described hollow cathode hollow channel, and carbonaceous material described in preheating and carrier gas pan feeding, cause the pyrolytic reaction of carbonaceous material; With
The plasma formed between the cathode bar of hybrid reaction section and anode and/or electric arc forming region are positioned at outside the reaction tube of described hybrid reaction section, the multiply plasma gas that multiply working gas enters described plasma and/or the generation of electric arc forming region through its entrance clashes near the reaction tube center of above-mentioned hybrid reaction section or its, and enter carbonaceous material in the reaction tube of above-mentioned hybrid reaction section and carrier gas pan feeding and its volatiles produced with the reaction tube by above-mentioned preheating section and carry out counter current contact and mix, the carbonaceous material of further heating preheating and carrier gas pan feeding, and impel described carbonaceous material generation pyrolysis, cracking and volatile matter gas-phase reaction.
2. reactor assembly according to claim 1, wherein, described multiple cathode bar and multiple anode corresponded are distributed in the surrounding of the reaction tube of described hybrid reaction section symmetrically.
3. reactor assembly according to claim 2, wherein, described cathode bar is even number with the quantity of the anode corresponded.
4. reactor assembly according to claim 3, wherein, described cathode bar is 4 with the quantity of the anode corresponded.
5. reactor assembly according to claim 1, wherein, at described preheating section, the minimum distance between described hollow cathode and described anode surface is 1-400 millimeter.
6. reactor assembly according to claim 1, wherein, described hollow cathode outer surface, cathode bar surface and at least part of region of anode interior are cooled medium circulation cooling, have cooling medium entrance and cooling medium outlet near it.
7. reactor assembly according to claim 1, wherein, the temperature of the plasma gas produced in described preheating section is guaranteed to make the temperature of the carbonaceous material entered in the reaction tube of preheating section reach 650 DEG C ~ 1250 DEG C; The temperature that the temperature of the multiply plasma gas produced in described hybrid reaction section guarantees to make to enter carbonaceous material in the reaction tube of hybrid reaction section or its volatiles reaches 1500 DEG C ~ 2900 DEG C.
8. reactor assembly according to claim 1, wherein, described working gas is becoming the high-temperature plasma gas of hydrogen, nitrogen, methane and/or inert gas after described plasma and/or electric arc forming region.
9. reactor assembly according to claim 1, wherein, the shock chilling medium entered in the reaction tube of hybrid reaction pars infrasegmentalis described in last guarantee product before leaving reaction tube by Quench to lower than 527 DEG C.
10. reactor assembly according to claim 1, wherein, carbonaceous material and/or the time of staying of volatiles in described preheating section and each section of hybrid reaction section are 0.4 ~ 4.0 millisecond.
, wherein, in described reactor assembly, there is carbonaceous material pyrolysis, the temporal summation of cracking and volatile matter gas-phase reaction and pyrolysis product Quench be less than 50 milliseconds in 11. reactor assemblies according to claim 1.
12. reactor assemblies according to claim 1, wherein, described shock chilling medium comprises: the carbonaceous material of aqueous water, water vapour, propane, aromatic compound, inert gas, any type and/or their mixture; Described carrier gas comprises: hydrogen, nitrogen, methane, gaseous carbon material, inert gas and/or their mixture.
13. reactor assemblies according to claim 1, wherein, described carbonaceous material is selected from coal, coal tar, coal directly-liquefied residue, heavy oil residue, Jiao, petroleum coke, oil-sand, shale oil, carbonaceous industrial waste or tailing, living beings, synthetic plastic, synthetic polymer, damaged tire, Municipal solid rubbish, pitch and/or their mixture.
14. reactor assemblies according to claim 1, wherein, the input power of described hollow cathode, cathode bar and/or anode is 5kW ~ 20MW, to form the electric arc producing plasma gas.
15. reactor assemblies according to claim 1, wherein, the volume ratio of described carbonaceous material and carrier gas is 10/90 ~ 90/10.
16. according to one of any described reactor assembly of claim 1-15, and wherein, described pyrolysis product comprises acetylene, carbon monoxide, methane, ethene and Jiao.
17. according to one of any described reactor assembly of claim 1-15, and wherein, the average grain diameter for the described carbonaceous material of cracking is 10 ~ 300 microns.
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CN105289442A (en) * 2015-11-16 2016-02-03 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) Reaction device for preparing acetylene by coal plasma pyrolysis
CN110591418A (en) * 2019-10-21 2019-12-20 中昊黑元化工研究设计院有限公司 Equipment and method for preparing carbon black by plasma countercurrent cracking of gaseous hydrocarbon
CN111100662A (en) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 Continuous operation method for microwave pyrolysis of waste plastics
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CN111100663A (en) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 Method for microwave pyrolysis of waste polyethylene
CN111100665A (en) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 Microwave pyrolysis method for vegetable oil
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CN111100661B (en) * 2018-10-29 2021-07-02 中国石油化工股份有限公司 Method for microwave pyrolysis of waste plastics
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