CN104785183B - A kind of multistage plasma pyrolysis carbonaceous material reactor assembly - Google Patents
A kind of multistage plasma pyrolysis carbonaceous material reactor assembly Download PDFInfo
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- CN104785183B CN104785183B CN201510171978.9A CN201510171978A CN104785183B CN 104785183 B CN104785183 B CN 104785183B CN 201510171978 A CN201510171978 A CN 201510171978A CN 104785183 B CN104785183 B CN 104785183B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 153
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 241
- 239000007789 gas Substances 0.000 claims abstract description 116
- 239000012159 carrier gas Substances 0.000 claims abstract description 52
- 238000010891 electric arc Methods 0.000 claims abstract description 51
- 238000005336 cracking Methods 0.000 claims abstract description 24
- 230000035939 shock Effects 0.000 claims abstract description 24
- 238000010791 quenching Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 238000010397 one-hybrid screening Methods 0.000 claims abstract description 3
- 239000011280 coal tar Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 36
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 24
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000003039 volatile agent Substances 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010574 gas phase reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000012546 transfer Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 8
- 239000002826 coolant Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000295 fuel oil Substances 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 3
- 239000003027 oil sand Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000003079 shale oil Substances 0.000 claims description 3
- 230000002123 temporal effect Effects 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 230000000712 assembly Effects 0.000 claims 5
- 238000000429 assembly Methods 0.000 claims 5
- 230000008021 deposition Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 63
- 230000035611 feeding Effects 0.000 description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 40
- 229910052786 argon Inorganic materials 0.000 description 20
- 238000004939 coking Methods 0.000 description 14
- 238000003776 cleavage reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- AURYFRZDONQWIG-UHFFFAOYSA-N 2-chloro-5-[2-(dimethylamino)ethyl]-11h-benzo[b][1,4]benzodiazepin-6-one;hydrochloride Chemical compound [Cl-].O=C1N(CC[NH+](C)C)C2=CC=C(Cl)C=C2NC2=CC=CC=C21 AURYFRZDONQWIG-UHFFFAOYSA-N 0.000 description 5
- 241001600609 Equus ferus Species 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000002296 pyrolytic carbon Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- -1 aromatic series Compound Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
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- 238000010530 solution phase reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a kind of multistage plasma pyrolysis carbonaceous material reactor assembly, system includes: a preheating section, and including hollow cathode and anode, carbonaceous material enters in preheating section reaction tube through the hollow channel of hollow cathode；At least one hybrid reaction section, including multiple cathode bars and multiple anodes corresponding with cathode bar, at least one shock chilling medium entrance, with at least one Quench product exit, wherein, the plasma formed between hollow cathode and anode and/or electric arc form district and are positioned in reaction tube, and the plasma formed between cathode bar and anode and/or electric arc form district and are positioned at outside reaction tube, head-on collision is there is and carries out counter current contact with carbonaceous material and carrier gas and strongly mix in multiply plasma gas near hybrid reaction section reaction tube center or its, the carbonaceous material of heating preheating, carbonaceous material is promoted to be pyrolyzed, cracking and volatile matter gas phase are reacted.Reactor assembly of the present invention has good anti-carbon deposition, the excellent thermal efficiency and the highest pyrolysis product productivity.
Description
Technical field
The present invention relates to a kind of carbonaceous material for cracking containing volatile matter to produce the high energy efficiency of high yield pyrolysis product
Apparatus and method, more particularly, it relates to a kind of multistage plasma pyrolysis carbonaceous material reactor assembly and utilize this multistage etc.
The method of plasma reactor system cracking carbonaceous material, more specifically it relates to one utilizes this multistage plasma reactor
System produces the method for acetylene.
Background technology
The product composition that carbonaceous material produces because of cracking or pyrolysis depends on reaction condition.It is known that some is specific
Reaction condition be conducive to the formation of some specific components, such as, when reaction zone temperature is higher than 1300K, be conducive to intermediate product second
The formation of alkynes.
It is said that in general, when electric arc is used as thermal source, arc-through gas, such as hydrogen, cause gas in very short time
Temperature increases to high degree, and the temperature of arc column can be usually reached 8000K～20000K.When gas leaves electric arc, temperature is usual
At about 2000K～5000K.With this understanding, gas molecule, such as hydrogen molecule may become hydrogen atom, even by partial dissociation
It is H+Or H-, thus produce high-temperature plasma gas.
Once high-temperature plasma gas leaves electric arc, and the atom of plasma gas or ion just recombine composition
The tendency that is exceedingly fast of son, so, they will discharge substantial amounts of heat.In addition to the sensible heat of plasma gas, the one of above-mentioned heat is big
Part is absorbed against the atom of plasma gas or the particles of carbonaceous material of ion by heat conduction, convection current and radiation, from
And cause particles of carbonaceous material to be pyrolyzed and/or crack, more specifically, cause particles of carbonaceous material to release its volatility
Point, i.e. devolatilization.
Known and it is confirmed that: with the difference of carbonaceous material type, the cracking of carbonaceous material and the step of devolatilization and bar
Part can great changes have taken place.Before this, because not knowing how that the cracking being obtained high yield by Solid carbonaceous material with rational cost is produced
The method of thing such as acetylene, so, gaseous state and liquid carbon material are the cracking pan feedings that people commonly use.Additionally gaseous state and liquid pan feeding
It is easily handled, and the loss to device of arc is relatively low.
In the prior art, for make to come from the productivity of some pyrolysis product of Solid carbonaceous material maximize and to equipment
The improvement carried out with technique, people have done a lot of trial and experiment.
US4358629 discloses a kind of arc reactor, and it includes four successively along the direction that solid carbonaceous material moves
Individual region, i.e. solid carbonaceous material powder dispersion area, arc region, reaction zone and chill zone.Owing to described powder is in arc region
The thermal inertia that the time of staying extremely short and described powder is the most temporary transient, the temperature of described powder is kept close to its temperature at entrance
Degree, and gas reaches the high temperature of 8000K, so, powder is only heated by gas by heat conduction, radiation and convection current at reaction zone.
So, all electric power are inputted by thin arc region, and the big energy that i.e. be enough to be improved by described powder temperature to more than 1800K causes
The irrational excessive gathering of energy, and inevitably by the beat exposure excessively concentrated on the wall of reactor, thus cause anti-
Answer wall overheated.The heat must removed near the wall of reactor for the wall of protection reactor accounts for the half of whole electric power input
Left and right waste as a result, a large amount of valuable energy is had to.Additionally, specific region occurs that reactor wall is tied by high temperature
The design of structure, the selection of wall material constitute great challenge, also make wall protection become a difficult problem.
CN103127895A discloses a kind of multistage plasma pyrolysis carbonaceous material reactor system with hollow cathode
System, every section of reactor assembly includes hollow cathode and the hollow anode of cooled medium circulation cooling；Working gas entrance；Carbon
Material and carrier gas pan feeding entrance；The reaction tube being connected with above-mentioned male or female, this external system also includes that at least one is positioned at
The shock chilling medium entrance of last reaction tube bottom；It is positioned at Quench product bottom last reaction tube with at least one
Outlet, wherein, forms one between the hollow cathode of first paragraph and hollow cathode and the anode of be used as reaction tube any one section
Individual generation plasma and/or the chamber of electric arc, plasma flow is near above-mentioned chamber highest temperature region or its and carbon
Material contacts fully with carrier gas pan feeding and/or volatiles and mixes, concurrent heat solution and/or gas phase reaction.
In above-mentioned multistage plasma pyrolysis carbonaceous material reactor assembly, owing to being formed between every section of hollow cathode and hollow anode
One chamber producing plasma and/or electric arc is all located in the reaction tube of each section, carbonaceous material and/or volatiles with
The plasma flow above-mentioned chamber highest temperature region in also being located at each section of reaction tube equally or its near carry out fully
Contact and mixing, although so substantially improving the thermal efficiency of reactor, but carbonaceous material or pyrolysis product in each section of reaction tube
Temperature is too high, and reacts in the case of tube wall do not has suitable safeguard measure, and this structure of reactor and pan feeding arrangement cause several
Unavoidable coking phenomenon, because pyrocarbon material powder or gaseous breakdown products contact the most continuously or wash away
The wall surface of reactor.
In above-mentioned existing plasma reactor, no matter how structure of reactor designs, and improves the thermal efficiency and cracking is produced
Produce rate almost becomes an implacable contradiction with eliminating the coking of reactor wall surface, accomplishes to improve the thermal efficiency the most simultaneously
With pyrolysis product productivity and eliminate the coking of reactor wall surface be one puzzlement industry a difficult problem.
By countless explorations and experiment, the present inventor is found that the technical scheme solving an above-mentioned difficult problem finally, thus develops
Go out to improve the thermal efficiency and pyrolysis product productivity simultaneously and eliminate the multistage plasma pyrolysis carbonaceous of reactor wall surface coking
Material reactor assembly and the method utilizing this multistage plasma reactor system cracking carbonaceous material.
Summary of the invention
The present invention provides a kind of multistage plasma pyrolysis carbonaceous material reactor assembly, and system includes:
One preheating section, including: the hollow cathode of cooled medium circulation cooling and anode；Be positioned at described hollow cathode or
Working gas entrance between anode surface, for make described working gas enter by above-mentioned hollow cathode and anode formed etc.
Gas ions and/or electric arc form district, so that described working gas becomes plasma, be used for preheating carbonaceous material and carrier gas enters
Material；Carbonaceous material and carrier gas pan feeding entrance, be positioned at one end of described hollow cathode, and the hollow channel of described hollow cathode is used as
Carbonaceous material and the transfer passage of carrier gas pan feeding, carbonaceous material and carrier gas pan feeding pass through described carbonaceous material through above-mentioned transfer passage
With carrier gas pan feeding entrance enter described preheating section reaction tube in；
At least one hybrid reaction section, is positioned under described preheating section, including the moon of multiple cooled medium circulation cooling
The most excellent and multiple and described cathode bar corresponding formation chamber housing one cathode bar cooled medium circulation cool down
Anode, described cathode bar and anode the plasma formed and/or electric arc form district and are positioned in the chamber that described anode is formed；
Working gas entrance between described cathode bar or anode surface, is used for making described working gas enter by above-mentioned cathode bar
The plasma formed with anode and/or electric arc form district, so that described working gas becomes plasma, for further
The carbonaceous material of heating preheating and carrier gas pan feeding, promote to be entered the reaction of described hybrid reaction section by the reaction tube of described preheating section
Carbonaceous material in pipe is pyrolyzed, cracks and the reaction of volatile matter gas phase；
At least one shock chilling medium entrance, for Quench or freeze product, is positioned at last described hybrid reaction
Pars infrasegmentalis；With at least one Quench product and the outlet of gas, it is positioned at described shock chilling medium entrance bottom,
Wherein, the plasma formed between hollow cathode and the anode of preheating section and/or electric arc form district and are positioned at described
In the reaction tube of preheating section, enter the carbonaceous material the reaction tube of above-mentioned preheating section and load from described hollow cathode hollow channel
Gas pan feeding forms district at described plasma and/or electric arc or contacts fully with the plasma gas produced near it
And mixing, and preheat described carbonaceous material and carrier gas pan feeding, cause the pyrolytic reaction of carbonaceous material；With
The plasma formed between cathode bar and the anode of hybrid reaction section and/or electric arc form district and are positioned at described mixing
Outside the reaction tube of conversion zone, multiply working gas forms what district produced through its entrance described plasma of entrance and/or electric arc
Multiply plasma gas clashes near the reaction tube center of above-mentioned hybrid reaction section or its, and with by above-mentioned pre-
The reaction tube of hot arc enters the carbonaceous material in the reaction tube of above-mentioned hybrid reaction section and carrier gas pan feeding and its pyrolysis produced
Volatile matter carries out counter current contact and mixing, the carbonaceous material of heating preheating further and carrier gas pan feeding, and promotes described carbonaceous material
Material is pyrolyzed, cracks and the reaction of volatile matter gas phase.
Preferably, in above-mentioned reactor assembly, the plurality of cathode bar and multiple corresponding anode are the most right
It is distributed in the surrounding of the reaction tube of described hybrid reaction section with claiming, it is highly preferred that described cathode bar and corresponding anode
Quantity be even number, such as, the quantity of described cathode bar and corresponding anode is 4.
Minimum distance generally, in above-mentioned reactor assembly, between hollow cathode and the anode surface of described preheating section
For 1-400 millimeter.At least part of region of described hollow cathode outer surface, cathode bar surface and anode interior medium that is cooled follows
Ring cools down, and has 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 guarantees to make
The temperature entering the carbonaceous material in the reaction tube of preheating section reaches 650 DEG C～1250 DEG C；Described hybrid reaction section produces
The temperature of multiply plasma gas guarantees to make the carbonaceous material in the reaction tube of entrance hybrid reaction section or its volatiles
Temperature reach 1500 DEG C～2900 DEG C.
Generally, in above-mentioned reactor assembly, described working gas is forming district through described plasma and/or electric arc
After become the high-temperature plasma gas of hydrogen, nitrogen, methane and/or inert gas；Enter last described hybrid reaction
Shock chilling medium in the reaction tube of pars infrasegmentalis guarantees that product is quenched to less than 527 DEG C before leaving reaction tube.
Preferably, in above-mentioned reactor assembly, carbonaceous material and/or volatiles are anti-at described preheating section and mixing
The time of staying in each section of the section of answering is 0.4～4.0 millisecond；In described reactor assembly occur carbonaceous material pyrolysis, cracking and
The temporal summation of the reaction of volatile matter gas phase and pyrolysis product Quench is less than 50 milliseconds.
Generally, in above-mentioned reactor assembly, described shock chilling medium includes: aqueous water, water vapour, propane, aromatic series
Compound, inert gas, any kind of carbonaceous material and/or their mixture；Described carrier gas includes: hydrogen, nitrogen, first
Alkane, gaseous carbon material, inert gas and/or their mixture；Described carbonaceous material is direct selected from coal, coal tar, coal
Liquefied residue, heavy oil residue, Jiao, petroleum coke, oil-sand, shale oil, carbonaceous industrial waste or tailing, living beings, synthetic plastic, conjunction
Become 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, in order 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 includes acetylene, carbon monoxide, methane, ethene and Jiao；Average particle for the described carbonaceous material of cracking
Footpath 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 existing descending plasma reactor system of single hop closed-entry.
In FIG, each reference numerals represents following meanings: 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-mixing is anti-
The section of answering 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 vent；21-preheating section hollow cathode；22,23-hybrid reaction section cathode bar；31-preheating section anode；32,33-mixing is anti-
The section of answering anode；41-preheating section preheating mixed zone；42-hybrid reaction section hybrid reaction district.
In fig. 2, each reference numerals represents following meanings: 11,14 or 214-hollow cathode；5,205 or 305-anode；4、
204 or 304-working gas entrances；1-carbonaceous material and carrier gas pan feeding entrance；14,214,314-reaction tube；15,215-insulation
Parts；8-shock chilling medium entrance；10-Quench product and gas vent；20-electric arc forms district；21-highest temperature region.
In figure 3, each reference numerals represents following meanings: 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, wherein corresponding shown in accompanying drawing or
Parts or the feature of equivalent represent by identical reference numerals.
It is said that in general, the reaction of the volatile matter discharged by pyrolytic carbon material, such as bituminous coal produces at pyrolysis product
In play an important role.Due to carbonaceous material experience and the gas of high reaction activity, the pole of such as high-temperature plasma gas
Fast reaction, and such reaction requires that moment is terminated, 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, it is then not possible to have the sufficient time to reach thermodynamic equilibrium.
For solid carbonaceous material, the heat transfer of carbonaceous material and pyrolysis, homogeneous gas-solid reaction and homogeneous gas phase
The speed of pyrolysis product formation, i.e. productivity will be affected.It is true that the main object of the present invention also includes making some specific cleavage
Product, as acetylene productivity maximize, therefore understand and determine that above-mentioned pyrolysis and the characteristic of reaction, mechanism and operating condition have been
Become one of key of the present invention.
Countless tests confirm: the pyrolysis temperature of carbonaceous material, particularly solid carbonaceous material is preferably 650 DEG C～1250
DEG C, such as 680-1100 DEG C, more preferably 700 DEG C～930 DEG C, particularly preferably 750 DEG C～900 DEG C, such as 850 DEG C, and by
The gas phase reaction temperature of the volatile matter that carbonaceous material obtains is preferably 1500 DEG C～2900 DEG C, more preferably 1500 DEG C～2500
DEG C, particularly preferably 1500 DEG C～2000 DEG C, for example, 1750 DEG C or 1850 DEG C.
Said temperature determine carbonaceous material experience pyrolysis and discharge volatile matter preferable temperature and subsequently volatile matter enter
The preferable temperature of promoting the circulation of qi phase reaction.In the present invention, carbonaceous material pyrolysis hollow cathode in described preheating section and anode it
Between formed in the region producing plasma and/or electric arc and just have started to, and the anticipated volatilization exceeding maximum growing amount 60%
Point it is to be formed in the reaction tube of above-mentioned preheating section, the gas phase of above-mentioned volatile matter reaction then main anti-in hybrid reaction section
Ying Guanzhong occurs.
In order to obtain the fastest and convert the most completely, the above-mentioned gas phase reaction time of described volatile matter
It is preferably less than 4 milliseconds, such as 2 milliseconds, more preferably less than 1 millisecond, particularly preferably less than 0.4 millisecond, such as less than 0.3 or 0.2
Millisecond.Such reaction time can ensure to obtain the high yield of pyrolysis product.
Generally speaking, the feasible method of the productivity improving pyrolysis product, particularly acetylene has following several:
First, primary volatile matter and at high-temperature plasma gas, such as plasma hydrogen and/or the inertia that includes helium
Reactivity in gas is high but the reaction height being exceedingly fast between plasma composition that the time-to-live is short to control some special
Determine pyrolysis product, productivity such as acetylene.Therefore, if the most rapidly pyrolytic carbon material and discharge high concentration or substantial amounts of
Volatile matter, the productivity of pyrolysis product will be higher, and this can be distributed by rationally selecting the ultra-fine grain diameter of carbonaceous material, or considers
Oxygen in volatile matter can be converted into carbon monoxide and consume acetylene, uses low-grade but that oxygen content is low carbonaceous material to come real
Existing.
Secondly, the optimum operation condition of pyrolytic carbon material is selected, in order to obtain the volatile matter of maximum quantity.Therefore, close
Suitable pyrolysis time, pressure and/or temperature is the key making described volatile matter growing amount reach maximum.
3rd, make above-mentioned volatile matter contact with the plasma composition of the most high reaction activities, do so and can increase
Reaction surface also improves reaction conversion ratio.
4th, the reaction temperature of volatile matter and high reaction activity plasma composition is another that affect pyrolysis product productivity
Individual key factor, it is however generally that, the productivity of pyrolysis product improves with the temperature that above-mentioned gas phase is reacted and increases, but too high reaction
Temperature can result in can cigarette ash-Jiao of quantitation and hydrogen.
Those of ordinary skill in the art from above analysis it is evident that: the pyrolysis of carbonaceous material and primary volatile matter with
The gas phase reaction of high reaction activity plasma composition is all the most important process forming pyrolysis product.But, pyrolysis is
Good technological parameter or operating condition are the most different from the optimal processing parameter that above-mentioned gas phase is reacted or operating condition, if as existing
The structure design of plasma reactor like that, i.e. carbonaceous material and the contact of plasma flow and mixing, carbonaceous material heat
Solve and the reaction of volatile matter gas phase occurs in the same space or region, be not only due to carbonaceous material and contact with plasma flow
Cause hot transfer efficiency to decline with the region of mixing away from high-temperature region, and be pyrolyzed technological parameter or the operation of gentle phase reaction
Condition is also unable to reach well balance and optimization.If exist in reaction tube simultaneously multiple formation high reaction activities etc. from
Daughter gas or the high-temperature region of electric arc, it will causing the volatile matter produced by carbonaceous material to carry out, that secondary response formed is burnt
Quantity increases, and these Jiao are attached on the wall of reactor, it will have a strong impact on the work of reactor.The how heat of concerted reaction device
Efficiency, product yield and the contradiction eliminated between the coking of reactor wall surface are extremely difficult problems.
For above-mentioned technical barrier, the present inventor is proposed by countless explorations and experiment and has been invented a kind of brand new
Multistage plasma reactor system, the multistage plasma reactor system invented makes above-mentioned pyrolysis gentle on the contrary dexterously
Should occur in different spaces or region, make the technological parameter of the gentle phase reaction of pyrolysis or operating condition reach optimum simultaneously, with
Time one high-temperature region forming high reaction activity plasma gas or electric arc is only set in the reaction tube of preheating section in advance
Hot 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.
As exemplary embodiment, as it is shown in figure 1, in multistage plasma reactor system of the present invention, in preheating section
The plasma formed between empty negative electrode 21 and anode 31 and/or electric arc form district and are positioned in the reaction tube of described preheating section, from
Described hollow cathode 21 hollow channel enter the carbonaceous material in the reaction tube of above-mentioned preheating section and carrier gas pan feeding described etc. from
Daughter and/or electric arc formed district or its near contact fully with the plasma gas produced herein and mix, and in advance
The described carbonaceous material of heat and carrier gas pan feeding, cause the pyrolytic reaction of carbonaceous material.
Equally, as it is shown in figure 1, in multistage plasma reactor system of the present invention, the cathode bar 22 of hybrid reaction section,
The plasma formed between 23 and anode 32,33 and/or electric arc are formed outside the reaction tube that district is positioned at described hybrid reaction section,
Multiply working gas enters the multiply plasma gas of described plasma and/or electric arc formation district's generation upper through its entrance
State the reaction tube center of hybrid reaction section or occur near it to clash and above-mentioned with by the reaction tube entrance of above-mentioned preheating section
Carbonaceous material in the reaction tube of hybrid reaction section and carrier gas pan feeding and its volatiles produced carry out counter current contact and
Strong mixing, the carbonaceous material of heating preheating further and carrier gas pan feeding, and promote described carbonaceous material to be pyrolyzed, crack and
Volatile matter gas phase is reacted.
The structure design of above-mentioned multistage plasma reactor system makes formed plasma flow above-mentioned pre-
Plasma and/or electric arc between hot arc hollow cathode and anode are formed in district, particularly in described formation district adjacent to electric arc
In the highest temperature region of post or neighbouring sufficiently contact with carbonaceous material and carrier gas pan feeding and mix, realizing quickly and
Cause pyrolysis while efficient heat transfer, and discharge volatile matter, along with the lasting of heat transfer and the carbonaceous material described mixing of entrance are anti-
In the reaction tube of the section of answering, the further concurrent heating of the multiply plasma produced outside the reaction tube of blended conversion zone and strong right
Stream mixes, and carbonaceous material and the volatile matter temperature formed promote further, and cause the gas phase of a large amount of volatile matter to react, thus
Produce various pyrolysis product, so, be pyrolyzed gentle phase reaction technological parameter and operating condition can be controlled independently of one another or
Selecting, also make them be optimised becomes possibility simultaneously.
As it is shown in figure 1, in preheating section, the position forming district and/or highest temperature zone of plasma and/or electric arc can
Changing by adjusting described hollow cathode 21, the position of anode 31, size and/or structural parameters, such adjustment can ensure that
Carbonaceous material and carrier gas pan feeding 1 and/or volatiles carry out the preheating being fully contacted and efficiently mixing with plasma flow
Region be positioned at described plasma and/or electric arc formed the highest temperature region in district or its near, thus realize quickly and efficiently
Heat transfer.Such as, the minimum distance between the surface of hollow cathode 21 and anode 31 is usually 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, described hollow cathode 21 He
At least part of region of cathode bar 22,23 outer surface and anode 31,32,33 be cooled medium circulation cooling, have cooling near it
Medium inlet 3,5,8 and 13 and cooling medium outlet 4,6,9 and 14.
In above-mentioned multistage plasma reactor system, pyrolysis temperature is usually 650 DEG C～1250 DEG C, and 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 the pre-thermal technology of pyrolysis
Make gas after forming district through plasma and/or electric arc, become the high temperature etc. of hydrogen, nitrogen, methane and/or inert gas
Plasma gas, through with carbonaceous material and the mixing of carrier pan feeding and heat transfer, carbonaceous material is preheated to 650 DEG C～1250
℃。
In order to prevent the pyrolysis product obtained by gas phase reaction, such as acetylene decomposition or occur secondary response to ultimately form at a low price
Cigarette ash-Jiao of value and hydrogen, the pyrolysis product generated must wink in the reaction tube bottom of hybrid reaction section last described
Between be quenched.It is said that in general, pyrolysis product is the most preferably quenched to 650 DEG C within 4 milliseconds, such as 2 milliseconds, preferably
600 DEG C, particularly preferred less than 527 DEG C.Described shock chilling medium preferably includes aqueous water, water vapour, propane, aromatic compound
Thing, inert gas, any kind of carbonaceous material 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 pan feeding in preheating section and hybrid reaction section
The time of staying, reaction time and the number of hybrid reaction section.More typically, the pyrolysis of generation in described reactor assembly,
The temporal summation of gas phase reaction and Quench is preferably less than 50 milliseconds.
In order to obtain ultra-fine grain or finely disseminated carbonaceous material excellent transmission efficiency and/or realize carbonaceous material with
Being sufficiently mixed or being in close contact of plasma flow, it usually needs for transmitting the carrier gas of particles of carbonaceous material or fine powder, and
And carrier gas can be selected from hydrogen, methane, nitrogen, gaseous carbon material, inert gas and/or their mixture.Inert gas
Exemplary embodiment be 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 the cross-sectional area of hollow cathode, preferably reaction tube is 1～3 times of the cross-sectional area of hollow cathode.This
The design of sample prevents pan feeding or thermal decomposition product directly wash away the inner surface of above-mentioned reaction tube and are formed on or build up Jiao.
Equally, in order to be evenly distributed or disperse carbonaceous material and carrier gas to enter in described reactor assembly inner space
Material, working gas (plasma gas), pyrolysis product and/or shock chilling medium, preferably: carbonaceous material and carrier gas pan feeding, work
The quantity of the entrance making gas (plasma gas), pyrolysis product and/or shock chilling medium can be multiple, and preferred
It is: above-mentioned entrance in the horizontal direction can be by symmetrical and be relatively arranged.
The carbonaceous material used in plasma reactor system of the present invention can be solid-state, liquid and/or gaseous material,
And preferably solid carbonaceous material, such as, it is selected from coal, coal tar, coal directly-liquefied residue, heavy oil residue, Jiao, oil
Jiao, 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, described hollow cathode 21, cathode bar 22,23 and anode 31,
32, the input power of 33 can be 1kW～20MW, for example, 5kW～10MW, in order to forms the electric arc producing plasma flow.
The details relevant to plasma generator is retrieved from or with reference to existing document, such as US4358629, CN1562922A or CN
101742808A, in order to save space, being described in detail in this and save about plasma generator.
Owing to carbonaceous material pyrolysis enters between above-mentioned preheating section hollow cathode 21 and preheating section anode 31 at carbonaceous material
The plasma formed and/or electric arc are formed in district or its neighbouring high-temperature region and just have started to, and are entering hybrid reaction section
Still continuing after in reaction tube, so carbonaceous material pyrolysis time is generally than mainly generation in the reaction tube of hybrid reaction section
Primary volatile matter contained with high-temperature plasma air-flow reactivity is high but the gas of plasma composition that the time-to-live is short
The time of phase reaction 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 district mixed
Territory close in preheating section reaction tube plasma and/or electric arc formed district highest temperature region or near, carbonaceous material
Temperature and its heated speed are greatly improved in preheating section, while realizing quickly and efficiently heat transfer, and carbonaceous material
Can discharge more volatile matter at short notice, this is conducive to forming more pyrolysis product in hybrid reaction section, meanwhile, wait from
Daughter and/or electric arc form district and highest temperature zone thereof and are positioned at the design in preheating section reaction tube and are also very beneficial for improving reaction
The thermal efficiency of device.
(2) owing to carbonaceous material is mainly preheated in preheating section and is pyrolyzed, its temperature is still not enough so that being pyrolyzed
The primary volatile matter produced and reactivity is high but it is anti-to carry out obvious gas phase between plasma composition that the time-to-live is short
Should, so, although the plasma being positioned in preheating section reaction tube and/or electric arc formation district and highest temperature zone temperature thereof are relatively
Height, but can not promote formed on reactor wall or build up substantial amounts of Jiao.
(3) carbonaceous material pyrolysis just has started in preheating section reaction tube, and is continued until that it enters hybrid reaction section
Reaction tube in after, therefore, carbonaceous material contacts with high-temperature plasma air-flow, mixes and is pyrolyzed in preheating section reaction tube
Time and the region time that occurs primary volatile matter gas phase react main from hybrid reaction section and region different, this will make
Gentle phase reaction must be pyrolyzed occur in different spaces or region, so that being pyrolyzed technological parameter or the operation bar of gentle phase reaction
Part may be adjusted independently of one another, and reach optimum simultaneously, and this becomes the conversion of pyrolysis product by being greatly improved carbonaceous material
Rate.
(4) in hybrid reaction section, multiply working gas is converted into multiply high-temperature plasma gas, and these multiplies are high
Isothermal plasma gas carry amount of heat enter hybrid reaction section reaction tube in after, at the reaction tube center of hybrid reaction section
Position or its near occur head-on collision and with by preheating section reaction tube enter hybrid reaction section reaction tube in carbonaceous material and
Carrier gas pan feeding and its volatiles produced carry out counter current contact and strong mixing, and bring up to reaction temperature rapidly promote
Carbonaceous material is made pyrolysis and cracking to occur, be particularly pyrolyzed the temperature that the primary volatile matter generation gas phase of generation is reacted, thus real
Show and conducted heat efficiently, quickly and uniformly between carbonaceous material and carrier gas pan feeding and high-temperature plasma air-flow.This will greatly
Improve productivity and the yield of pyrolysis product, particularly acetylene.
(5) although reaction temperature is higher in the reaction tube of hybrid reaction section, but different from preheating section, in hybrid reaction section
In, owing to being formed district and highest temperature zone thereof not in mixing by the plasma produced between cathode bar and anode and/or electric arc
In the reaction tube of conversion zone, and in the chamber formed by anode, produced multiply high-temperature plasma air-flow carries greatly
After calorimetric amount leaves the reaction tube that multiple such chamber enters hybrid reaction section, just the pyrolysis with carbonaceous material and generation thereof is waved
Send out to divide and contact and mix, the most both ensure that the reaction tube of hybrid reaction section has sufficiently high reaction temperature, prevented again
Stop in the reaction tube that the excess calories of high-temperature plasma torch concentrates on hybrid reaction section, caused the concentrations of heat release not
Appear in reaction tube, thus avoid serious energy waste and a large amount of coking and too high occurs near reactor wall
Temperature Distribution.
(6) in multistage plasma reactor system of the present invention, preheating section and the diverse structure of hybrid reaction section
Design makes multistage plasma reactor system of the present invention solve the reactor assembly thermal efficiency, cleavage reaction product well
Yield and the contradiction eliminated between the coking of reactor wall surface.
Multistage plasma reactor system of the present invention can be used for producing the pyrolysis product from various carbonaceous materials, allusion quotation
The method of type is as described below:
A) carbonaceous material is incorporated in preheating section reaction tube, in advance through the hollow channel of described hollow cathode by means of carrier gas
Generation plasma and/or the region of electric arc being positioned at preheating section reaction tube is formed between hollow cathode and the anode of hot arc；
B) the working gas entrance between hollow cathode or anode, is incorporated into above-mentioned generation plasma by working gas
And/or in the region of electric arc, working gas subsequently when the electric arc that passes through between hollow cathode and anode forms district by plasma
Body, and near above-mentioned generation plasma and/or the region of electric arc or its highest temperature region or its with from hollow cathode
Hollow channel enters the carbonaceous material in above-mentioned preheating section reaction tube and carrier gas pan feeding is fully contacted and mixes, and causes heat
Solve 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 subsequently enters mixing
In the reaction tube of conversion zone, multiply working gas enters by generation between cathode bar and the anode of hybrid reaction section through its entrance
Plasma and/or electric arc form district, and are in plasma when passing through above-mentioned electric arc formation district, the multiply plasma of generation
Gas carries after amount of heat enters in the reaction tube of hybrid reaction section, in the reaction tube center of hybrid reaction section or it is attached
Near occur head-on collision and with the carbonaceous material in the reaction tube being entered hybrid reaction section by the reaction tube of preheating section and carrier gas pan feeding with
And the volatiles produced carries out counter current contact and strong mixing, and bring up to promote carbonaceous material by reaction temperature rapidly
There is pyrolysis and cracking, be particularly pyrolyzed the temperature that the primary volatile matter generation gas phase of generation is reacted, thus promote in mixing anti-
The reaction tube of the section of answering occurs carbonaceous material cracking reaction, particularly volatile matter gas phase reaction, thus produces cracking and/or pyrolysis
Product；
D) through described shock chilling medium entrance, shock chilling medium is incorporated into the bottom of last hybrid reaction section reaction tube, with
Just Quench or freeze described cracking and/or thermal decomposition product；
E) will crack and/or thermal decomposition product, gas through Quench product and gas vent, and/or the carbonaceous material of pyrolysis will be residual
Excess discharges described reactor or reaction tube.
It is said that in general, the pyrolysis product of carbonaceous material is mixture, it includes acetylene, carbon monoxide, methane, ethene, hydrogen
Gas and Jiao etc., if it is desired to obtain some specific cleavage product, such as acetylene, it is necessary to separate the mixture of described pyrolysis product, with
Just the purest pyrolysis product is obtained.Such as, bibliography US4367363 discloses and divides from above-mentioned cleavage product mixtures
Separate out the separation method of pure acetylene.In order to save space, it be described in detail in this save about separate.
In order to obtain carbonaceous material pyrolysis and the optimum efficiency of cracking, except the structure of plasma reactor system designs
Outward, also should consider or select physics and the chemical property of pan feeding further, in order to make the productivity of pyrolysis product reach maximum.Typically
For, the average grain diameter of carbonaceous material is preferably 10～300 microns, and carbonaceous material temperature before entering described reactor assembly
Degree is preferably 20～300 DEG C.The volume ratio of carbonaceous material and carrier gas is generally 10/90～90/10, preferably 20/80～80/
20, more preferably 30/70～70/30, particularly preferably 40/60～60/40, such as 50/50.
Finally, it will also be clear that: carbonaceous material and/or the heated speed of volatiles are preferably greater than 104The K/ second, and
And in order to the flexibility operated and under various circumstances to operation different demands, described hollow cathode, cathode bar, anode and/
Or their position, size and/or structural parameters are adjustable in.
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 for coal tar
It is converted into acetylene and other chemicals.Using the coal tar of generation during a kind of pyrolysis of coal as carbonaceous material pan feeding, its character
As shown in table 1.
Table 1
In the invention described above multistage plasma reactor system, the hollow cathode 21 of preheating section and plasma torch thereof
Input power be 5kW, the input power of four cathode bars of hybrid reaction section 22 and 23 and plasma torch thereof is all 5kW,
Produce an arc region of plasma to be formed at preheating section and form four of generation plasma in hybrid reaction section
Arc region.
As it is shown in figure 1, the coal tar pan feeding 1 of 300K is through hollow channel quilt under the conveying of argon carrier of hollow cathode 21
Being incorporated in described preheating section reaction tube, volume ratio is that the argon hydrogen mixture working gas of 4:6 is introduced in through its entrance 2
The arc region formed by hollow cathode 21 and anode 31 in preheating section reaction tube is in plasma, wherein, coal tar pan feeding
The region 41 closing on arc column with plasmarized working gas in preheating section arc region is rapidly mixed, thus rapidly by coal
Tar pan feeding preheats, and rises to proceed by the temperature of pyrolytic reaction by its temperature.
Afterwards, the volatile matter that coal tar pan feeding 1, argon carrier and pyrolysis produce is downwardly into the reaction tube of hybrid reaction section
In, the argon hydrogen mixture working gas that four bursts of volume ratios are similarly 4:6 is introduced in hybrid reaction section through its entrance 7 and 12
It is in plasma by cathode bar 22 and 23 and four arc region being formed of anode 32 and 33, consequent four strands of high temperature etc.
Gas ions air-flow enters and is positioned at the reaction tube center of hybrid reaction section or near zone 42 clashes, and with by preheating section
Reaction tube enter hybrid reaction section reaction tube in coal tar pan feeding, carrier gas and volatiles carry out counter current contact and
Strong mixing, and bring up to reaction temperature rapidly promote coal tar pyrolysis and cracking to occur further, particularly makes pyrolysis produce
The temperature of raw primary volatile matter generation gas phase reaction, thus form a large amount of cleavage reaction product, such as acetylene.
The shock chilling medium of the reaction tube bottom that cleavage reaction product, such as acetylene are entered hybrid reaction section through its entrance 17
Quench or freeze, after be discharged reactor through the outlet 18 of Quench product and gas.
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, and argon carrier flow is 125g/h, argon in preheating section
Hydrogen mixture working gas flow 500g/h, in hybrid reaction section, per share argon hydrogen mixture working gas flow is
200g/h.It is anti-that coal tar enters mixing after being preheated by the plasma flow of argon hydrogen mixture in the reaction tube of preheating section
In the reaction tube of the section of answering, wherein, being 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 in the reaction tube of preheating section and hybrid reaction section with high-temperature plasma
Body air-flow carries out quick, efficient and uniformly mixes and after heat transfer, produce substantial amounts of cleavage reaction product.Aqueous water is situated between as Quench
Matter is injected into the reaction tube bottom of hybrid reaction section through being positioned at the shock chilling medium entrance 17 near pyrolysis product outlet 18, in order to
Moment Quench or freeze formed cleavage reaction product stream, shock chilling medium-liquid velocity is 40kg/h.Coal tar is in reaction
Total residence time in device system is about 30 milliseconds.The energy efficiency of described reactor is about 80% through measuring and calculating, say, that defeated
Enter the 80% of power and absorb by reacting product stream with for cooling down the water of plasma reactor wall, wherein caused by reaction tube
Heat loss be about 4kW.
Comparative example 1
Schematic diagram is that the reactor assembly of three sections of plasma pyrolysis carbonaceous materials with hollow cathode of Fig. 2 is used for
Coal tar is converted into acetylene and other chemicals.Use with the identical coal tar of use in embodiment 1 as carbonaceous material
Pan feeding.
The input of the plasma torch that above-mentioned three sections of plasma reactor system first paragraph hollow cathodes and anode are formed
The input power of the plasma torch that power is 5kW, second segment and the 3rd section of hollow cathode and anode are formed is all 10kW, in order to
Form the electric arc producing plasma.As in figure 2 it is shown, described reactor assembly is mainly by hollow cathode 11,14 and 214, anode
5,205 and 305, the entrance 4,204 and 304 of working gas, be used as the reaction tube 14 of second segment hollow cathode and be used as
The reaction tube 214 of three sections of hollow cathodes and the 3rd section of reaction tube 314, the entrance of shock chilling medium 8 and the outlet of the cold product of Quench 10
Composition, wherein, the nearest level between hollow cathode 11,14 and 214 outer surface and described anode 5,205 and the inner surface of 305
Distance d1It it is 12 millimeters；Between hollow cathode 11,14 and 214 outer surface lower end and described anode 5,205 and the inner surface of 305
Minimum distance d2It is respectively 8 millimeters；The sidewall 13,213 and 313 of described anode 5,205 and 305 and diapire 9,209 and 309 interior
Surface forms 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 diameters are 14 millimeters, and wall thickness is 2 millimeters；A length of 30 millimeters.The wall of described reaction tube 14,214 and 314 is at top
Near be made up of copper, other regions are made up of steel, utilize in the anchor ring gap between described wall and its protection overcoat high simultaneously
The water of speed circulation cools down the wall of described reaction tube 14,214 and 314.Respectively with one between reaction tube 14,214 and anode 5,205
Individual insulating element 15,215 holds physical isolation.
Using coal tar used in embodiment 1 as the carbonaceous material pan feeding of this comparative example 1, the coal tar warp of 300K
The hollow channel of hollow cathode 11,14 and 214 is introduced in described first paragraph, second segment and the 3rd section together with argon carrier
In chamber, volume ratio is that the argon hydrogen mixture working gas 4,204 and 304 of 4:6 is also introduced into above-mentioned three through its entrance
In individual chamber, and being in plasma, in above three chamber, coal tar and/or volatiles are with plasmarized
Working gas is rapidly mixed in the region closing on arc column and is heated rapidly, and causes the pyrolysis of coal tar and cracking anti-
Should, the particularly gas phase reaction of volatiles.
Above-mentioned three sections of plasma reactor systems with hollow cathode are run: system pressure under following operating condition
For 110kPa, the power output of first paragraph hollow cathode 11 and anode 5 is 5kW, second segment and the 3rd section of hollow cathode 14,214
Being all 10kW with the power output of second segment and the 3rd section of anode 205,305, coal tar flow 9kg/h, argon carrier flow is
125g/h, is divided into every part of stream of argon hydrogen mixture that volume ratio is 4:6 of the working gas 4,204 and 304 of impartial three parts
Amount is 430g/h.Argon hydrogen mixture be in plasma as working gas 4,204 and 304 after near the district of arc column
Territory temperature is about 3000K, coal tar and argon carrier pan feeding and/or volatiles from three hollow cathodes 11,14 and 214
Hollow channel enters in above three chamber, and wherein, the hot-cast socket factor reaches about 86%, high-temperature plasma air-flow with coal tar
Oil and carrier gas pan feeding and/or volatiles enter in three reaction tubes 14,214 and 314 after efficiently mixing.Water is through two
Pyrolysis product outlet 10 near shock chilling medium entrance 8 be injected in last reaction tube 314, in order to moment Quench or
Freeze formed reacting product stream.Coal tar total residence time in reactor assembly is about 30 milliseconds.Described reactor
The energy efficiency of system is about 82%, say, that the 82% of input power is by reacting product stream and is used for cooling down plasma
The water of reactor wall is absorbed, and the heat loss wherein caused by reaction tube is about 1.0kW.
Comparative example 2
Schematic diagram is that the reactor assembly of the single hop closed-entry descending plasma pyrolysis carbonaceous material of Fig. 3 is used for coal
Tar conversion is acetylene and other chemicals.Use with the identical coal tar of use in embodiment 1 as carbonaceous material pan feeding.
In the above-mentioned descending plasma reactor system of single hop closed-entry, produce and entered in reactor by its entrance 2
The input power of the plasma torch of high-temperature plasma gas is 25kW, produces the work gas of above-mentioned high-temperature plasma gas
Body be volume ratio be the argon hydrogen mixture of 4:6.
As it is shown on figure 3, the closed-entry passage at coal tar and argon carrier pan feeding 1 reacted device top enters in reactor,
Wherein, coal tar and argon carrier pan feeding with enter the high-temperature plasma gas in reactor in the reactor through its entrance 2
Quickly mix and conduct heat, thus rapidly coal tar being heated, and rise to its temperature to cause Coal Tars reaction and
The temperature of cracking reaction, particularly promote volatiles to carry out the temperature of gas phase reaction, thus produce a large amount of cracking reaction and produce
Thing, such as acetylene.
Cleavage reaction product, such as acetylene are entered the shock chilling medium Quench of reactor lower part or are freezed through its entrance 3,
It is discharged reactor by the outlet 4 of Quench product and gas.
The above-mentioned descending plasma reactor system of 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, and argon carrier flow is 125g/h, for producing
The argon hydrogen mixture working gas flow stating high-temperature plasma gas is 1300g/h.Wherein, in the district near arc column
Territory working gas temperature is about 3000K, and the hot-cast socket factor is about 75%.
Coal tar, carrier gas and/or volatiles in the above-mentioned descending plasma reactor of single hop closed-entry with high temperature
After plasma flow quickly mixes and conducts heat, produce substantial amounts of cleavage reaction product.Aqueous water is as shock chilling medium warp
It is positioned at the shock chilling medium entrance 3 near pyrolysis product outlet 4 and is injected into reactor lower part, in order to moment Quench or freeze institute's shape
The cleavage reaction product stream 5 become, shock chilling medium-liquid velocity is 40kg/h.Coal tar total residence time in the reactor
It is about 30 milliseconds.The energy efficiency of described reactor is about 70% through measuring and calculating, say, that the 70% of input power is produced by reaction
Logistics and the water for cooling down plasma reactor wall are absorbed, and the heat loss wherein caused by reaction tube is about 5kW.
The performance of the different types of reactor assembly of above three arranges 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-C2H2 | 8.1 | 7.4 | 17.2 |
| Methane production, g/kg coal tar | 165 | 56 | 76.9 |
| Carbon monoxide productivity, g/kg coal tar | 232 | 46 | 86.3 |
| Carbon is to gaseous product conversion ratio, % | 76.46 | 58.25 | 31.68 |
| C in product stream2H2Volume 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, SER refers to always ratio energy demand (the gross Specific on the basis of the electric power that electrode is transmitted
Energy Requirement)；Carbon to gaseous product conversion ratio refers to carbon in gaseous product and the containing of carbon in coal tar
Amount ratio；Energy efficiency refers to the relative populations of the heat absorbed by product stream and cooling water compared with input power.
Experimental data from table 2: the reactor assembly of multistage plasma pyrolysis carbonaceous material of the present invention (is implemented
Example 1) with the reactor assembly (comparative example 1) of existing three sections of plasma pyrolysis carbonaceous materials with hollow cathode and showing
The reactor assembly (comparative example 2) having single hop closed-entry descending plasma pyrolysis carbonaceous material is compared, in reactor system
Reach between the system thermal efficiency (energy efficiency), cleavage reaction product (acetylene) yield and elimination reactor wall surface coking (coking rate)
Arrive good equilibrium, overcome that acetylene yield and energy efficiency in comparative example 1 are high completely but coking is serious and contrast is real
Execute that coking rate in example 2 is low but acetylene yield and the highest defect of energy efficiency.
Term and form of presentation used by this specification are merely used as descriptive and nonrestrictive term and statement side
Formula, is not intended to the feature represented and describe or any equivalent of its part when using these terms and form of presentation
Exclusion.
Although having show and described several embodiments of the invention, but the present invention being not limited to described enforcement
Mode.On the contrary, those of ordinary skill in the art are it should be recognized that can be to this in the case of without departing from principle of the present invention and spirit
A little embodiments carry out any accommodation and improvement, and protection scope of the present invention is true by appended claim and equivalent institute thereof
Fixed.
Claims (17)
1. a multistage plasma pyrolysis carbonaceous material reactor assembly, reactor assembly includes:
One preheating section, including: the hollow cathode of cooled medium circulation cooling and anode；It is positioned at described hollow cathode or anode
Working gas entrance between surface, the plasma formed by above-mentioned hollow cathode and anode for making described working gas enter
Body and/or electric arc form district, so that described working gas becomes plasma, are used 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, and the hollow channel of described hollow cathode is used as carbon
Material and the transfer passage of carrier gas pan feeding, carbonaceous material and carrier gas pan feeding through above-mentioned transfer passage by described carbonaceous material and
Carrier gas pan feeding entrance enters in the reaction tube of described preheating section；
At least one hybrid reaction section, is positioned under described preheating section, including the cathode bar of multiple cooled medium circulation cooling
The anode cooled down with multiple and described cathode bar corresponding formation chamber housing one cathode bar cooled medium circulation,
The plasma formed by described cathode bar and anode and/or electric arc form district and are positioned in the chamber that described anode is formed；It is positioned at
Working gas entrance between described cathode bar or anode surface, is used for making described working gas enter by above-mentioned cathode bar and sun
Plasma and/or electric arc that pole is formed form district, so that described working gas becomes plasma, for heating further
The carbonaceous material of preheating and carrier gas pan feeding, promote by the reaction tube of the reaction tube described hybrid reaction section of entrance of described preheating section
Carbonaceous material be pyrolyzed, crack and volatile matter gas phase reaction；
At least one shock chilling medium entrance, for Quench or freeze product, is positioned under last described hybrid reaction section
Portion；With
At least one Quench product and the outlet of gas, be positioned at described shock chilling medium entrance bottom,
Wherein, the plasma formed between hollow cathode and the anode of preheating section and/or electric arc form district and are positioned at described preheating
In the reaction tube of section, enter the carbonaceous material the reaction tube of above-mentioned preheating section from described hollow cathode hollow channel and carrier gas enters
Expect form district at described plasma and/or electric arc or contact fully with the plasma gas produced and mixed near it
Close, and preheat described carbonaceous material and carrier gas pan feeding, cause the pyrolytic reaction of carbonaceous material；With
The plasma formed between cathode bar and the anode of hybrid reaction section and/or electric arc form district and are positioned at described hybrid reaction
Outside the reaction tube of section, multiply working gas enters described plasma and/or the multiply of electric arc formation district's generation through its entrance
Plasma gas clashes near the reaction tube center of above-mentioned hybrid reaction section or its, and with by above-mentioned preheating section
Reaction tube enter above-mentioned hybrid reaction section reaction tube in carbonaceous material and carrier gas pan feeding and its produce pyrolysis devolatilization
Divide and carry out counter current contact and mixing, the carbonaceous material of heating preheating further and carrier gas pan feeding, and promote described carbonaceous material to send out
Heat solution, cracking and the reaction of volatile matter gas phase.
Reactor assembly the most according to claim 1, wherein, the plurality of cathode bar and multiple corresponding anode
It is distributed in the surrounding of the reaction tube of described hybrid reaction section symmetrically.
Reactor assembly the most according to claim 2, wherein, the quantity of described cathode bar and corresponding anode is
Even number.
Reactor assembly the most according to claim 3, wherein, the quantity of described cathode bar and corresponding anode is
4。
Reactor assembly the most according to claim 1, wherein, at described preheating section, described hollow cathode and described anode
Minimum distance between surface is 1-400 millimeter.
Reactor assembly the most according to claim 1, wherein, described hollow cathode outer surface, cathode bar surface and anode
Internal at least part of region is cooled medium circulation cooling, has cooling medium entrance and cooling medium outlet near it.
Reactor assembly the most according to claim 1, wherein, the temperature of the plasma gas produced in described preheating section
Guarantee to make the temperature of the carbonaceous material in the reaction tube of entrance preheating section reach 650 DEG C～1250 DEG C；In described hybrid reaction section
The temperature of the multiply plasma gas produced guarantees to make the carbonaceous material in the reaction tube of entrance hybrid reaction section or its pyrolysis
The temperature of volatile matter reaches 1500 DEG C～2900 DEG C.
Reactor assembly the most according to claim 1, wherein, described working gas through described plasma and/or
Electric arc becomes the high-temperature plasma gas of hydrogen, nitrogen, methane and/or inert gas after forming district.
Reactor assembly the most according to claim 1, wherein, enters the reaction of last described hybrid reaction pars infrasegmentalis
Shock chilling medium in pipe guarantees that product is quenched to less than 527 DEG C before leaving reaction tube.
Reactor assembly the most according to claim 1, wherein, carbonaceous material and/or volatiles are at described preheating section
The time of staying in each with hybrid reaction section period is 0.4～4.0 millisecond.
11. reactor assemblies according to claim 1, wherein, occur carbonaceous material to be pyrolyzed in described reactor assembly,
The temporal summation of cracking and the reaction of volatile matter gas phase and pyrolysis product Quench is less than 50 milliseconds.
12. reactor assemblies according to claim 1, wherein, described shock chilling medium includes: aqueous water, water vapour, third
Alkane, aromatic compound, inert gas, any kind of carbonaceous material and/or their mixture；Described carrier gas includes: hydrogen
Gas, nitrogen, methane, gaseous carbon material, inert gas and/or their mixture.
13. reactor assemblies according to claim 1, wherein, described carbonaceous material is direct selected from coal, coal tar, coal
Liquefied residue, heavy oil residue, Jiao, petroleum coke, oil-sand, shale oil, carbonaceous industrial waste or tailing, living beings, synthetic plastic, conjunction
Become polymer, damaged tire, Municipal solid rubbish, pitch and/or their mixture.
14. reactor assemblies according to claim 1, wherein, the input of described hollow cathode, cathode bar and/or anode
Power is 5kW～20MW, in order 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 be 10/90～
90/10。
16. according to the reactor assembly described in any one of claim 1-15, and wherein, described pyrolysis product includes acetylene, an oxygen
Change carbon, methane, ethene and Jiao.
17. according to the reactor assembly described in any one of claim 1-15, wherein, for described carbonaceous material flat of cracking
All particle diameters are 10～300 microns.
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