CN104946281A - Device and method for intensifying tar cracking in biomass gasification pyrolysis process - Google Patents
Device and method for intensifying tar cracking in biomass gasification pyrolysis process Download PDFInfo
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- CN104946281A CN104946281A CN201510367575.1A CN201510367575A CN104946281A CN 104946281 A CN104946281 A CN 104946281A CN 201510367575 A CN201510367575 A CN 201510367575A CN 104946281 A CN104946281 A CN 104946281A
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- 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
- Y02P20/10—Process efficiency
Abstract
The invention discloses a device and a method for intensifying tar cracking in biomass gasification pyrolysis process. The device consists of a microwave generation device and a triggering discharge device, wherein microwaves generated from the microwave generation device are input into the triggering discharge device through waveguide; the triggering discharge device is internally provided with metal mediums Fe, Ni, Co or other alloys; the triggering discharge device is arranged in an area at the temperature of 200-800 DEG C on a biomass gasification pyrolysis device. The method is convenient to implement, a biomass gasification pyrolysis process does not need to be greatly adjusted or changed, no high temperature area is needed, and only a metal discharge area needs to be arranged. No catalyst is needed, so that the problem of catalyst deactivation can be avoided. Due to high-efficiency conversion of tar, problems of equipment blocking or corrosion caused by tar can be reduced or eliminated, the yield of a biomass gas can be increased, the quality of the biomass gas can be improved, and thus the energy utilization efficiency can be improved.
Description
Technical field
The present invention relates to a kind of electric discharge phenomena utilizing microwave and metal interaction to produce and carry out the coal-tar middle oil novel method removed of enhanced biological matter pyrolytic gasification process, be specifically related to the apparatus and method strengthening coke tar cracking in a kind of gasifying biomass pyrolytic process.
Background technology
(generation of tar)
Growing along with social energy demand, fossil oil as energy main source but reduces rapidly, therefore, sustainable and the eco-friendly substitute energy of development and utilization has become global key subjects, and biomass energy day by day becomes the focus paid attention to countries in the world as metastable renewable energy source.Biomass energy utilizes technology to comprise direct combustion, gasification and liquefaction three kinds of main paties, gasifying biomass is wherein the main switch technology of one that biomass energy GOOD TASTE utilizes, solid-state biomass fuel reburning can be become the inflammable gas of GOOD TASTE by it, is convenient to transmission, reprocessing and utilizes; And thermochemical conversion technology have energy transformation ratio high, be easy to industrialized advantage, be one of main technological development direction.But in current most widely used fixed bed gasification and fluidized bed gasifying process, pyrolytic gasification temperature great majority, all lower than 1000 DEG C, cause the existence of macromole tar in gaseous product to be difficult to avoid.The generation of tar and existing not only can cause the waste of the energy also can serious harm processing unit.On the one hand, the generation of tar reduces the Conversion of energy utilising efficiency of biomass, and the energy of tar generally accounts for the 5%-15% of biomass total energy, and this part energy is wasted because being difficult to be utilized; On the other hand, tar is the viscous liquid formed under condensation in fuel gas transmission process, is attached on the wall of pipeline and equipment, will causes blocking and the corrosion of pipeline, badly influence the normal operation of equipment; Moreover the carbon black that tar produces when burning also can cause and further pollute and equipment damage.Therefore, the generation of tar, control and form transformation are the critical problems in biomass pyrogenation gasification technical development.
(problem of prior art, it is difficult to control)
In biomass pyrogenation gasification technique, except generate angle development Sources controlling technology from tar except, after current common gasification, tar removal methods comprises mechanical means, pyrolysis method and catalystic pyrolysis.Mechanical means mainly relies on the physical process such as inertia, absorption and sorption, condensation to realize seizure and the transfer of tar ingredients, is tar is transferred to frozen state to reduce the impact on process system from gaseous state, the not basic removal of tar ingredients.Thermo-cracking and catalytic cracking method are normally created reaction conditions and are impelled tar ingredients generation cracking or reforming reaction, fundamentally reduce tar ingredients and exist.Thermo-cracking needs 1200 DEG C of even higher temperature condition, improves running cost, from balance energy utilization rate angle, although the required temperature of catalytic pyrolysis is lower there is the problems such as the easy carbon distribution of catalyzer, wearing and tearing, inactivation.Current, various tar minimizing technology is all in constantly research and development.
Summary of the invention
The object of the invention is, the apparatus and method strengthening coke tar cracking in a kind of gasifying biomass pyrolytic process are provided, remove problem for solving above-mentioned tar new technique approach is provided.
To achieve these goals, the present invention adopts following technical scheme:
A device for coke tar cracking is strengthened, by microwave generating apparatus and excite electric discharge device to form in gasifying biomass pyrolytic process.The microwave that described microwave generating apparatus produces excites electric discharge device by waveguide input; Described exciting in electric discharge device has transiting state metal or its alloy or its Nano/micron state particle, on the described flue exciting electric discharge device to be arranged on gasifying biomass pyrolysis installation, temperature is the region of 200 DEG C-800 DEG C, described in excite electric discharge device to be coordinated by metallic substance and non-absorbing material to make.
Described transiting state metal is Fe, Ni, Co, Cu.
Described metal form is strip, spination, spherical, needle-like, prickle shape or Nano/micron Granular composite are carried on medium, and described medium is SiO
2or Al
2o
3deng microwave transparency high temperature material.
Described exciting in electric discharge device can also arrange that loading type iron sill, carried copper-base, activated carbon or activated coke etc. are to strengthen microwave action.
Described non-absorbing material is that the absorbing property such as quartzy class, corundum class is weak and the material that resistance to elevated temperatures is strong.
The described electric discharge device that excites adopts Polygons or volution.
Described microwave generating apparatus can be the low-power magnetron combination of multiple about 1KW, also can be the high power magnetron of more than 10KW.
The simulator of coke tar cracking is strengthened in a kind of gasifying biomass pyrolytic process, by gas cylinder, laboratory push-and-pull syringe pump, digital display constant temperature electric heating cover, microwave oven, quartz reactor forms, described gas cylinder, digital display constant temperature electric heating cover, quartz reactor is connected in turn by pipeline, described digital display constant temperature electric heating cover is connected with laboratory push-and-pull syringe pump, described quartz reactor is arranged in described microwave oven, the glass wool of the shape identical with its bore is covered with bottom described quartz reactor, described glass wool tiles one deck quartz sand (for playing the effect of guard reactor and insulation, the amount of quartz sand is moderate, accumulation of heat is limited very little, gas heat absorption superdistension, too many then occupy the too many volume of reactor, have compressed the amount of reactant gases), described quartz reactor flange is fixed.
Pipeline between described gas cylinder and digital display constant temperature electric heating overlap arranges glass rotameter.
Described pipeline is silicone tube.
In described quartz reactor, reacted gas is connected with gas chromatograph with infrared spectrometer respectively by the threeway on pipeline.
The method of coke tar cracking is strengthened in a kind of gasifying biomass pyrolytic process, the section of flue-gas temperature 200 DEG C-800 DEG C in biomass pyrogenation gasification device, the electric discharge phenomena strengthening coke tar cracking utilizing microwave field and metal interaction to produce, described microwave frequency is 2450MHz or 915MHz.
According to the difference of biomass char oil nature and the needs of production process, water vapour, the carbonic acid gas or air etc. of different concns can also be passed at electrical discharge zone, to control the chemical constitution of coke tar cracking gas.
Microwave power controls can select 0.1W-100W/cm according to gaseous constituent and tar character
3.
Beneficial effect of the present invention:
The present invention uses a kind of novel method to realize the selective reinforcement cracking of tar in biomass pyrogenation gasification device, reduces the component content that biogas is coal-tar middle oil, promotes the Improvement and perfection of biomass pyrogenation gasification technique.The electric discharge phenomena that method of the present invention utilizes microwave field and metal interaction to produce, to mould a kind of local strengthening reaction environment, realize quick, the high strength cracking of biomass char oil component.The metal of particular type, specific modality is placed in microwave field, intensity can be produced differ under microwave electromagnetic field action, include the comprehensive electric discharge phenomena of the various ways such as corona discharge, arc discharge, glow discharge, dark discharge, this discharge process can directly produce high temperature hotspot effect on the one hand, the high temperature of 1000-2000 DEG C can be formed at electrical discharge zone, plasma body can be produced in local on the other hand, be presented as plasma effect, also can along with light-catalyzed reaction.Heat effect, plasma effect and photocatalytic effect these three kinds effect coupling superposition, can impel the rapid cleavage of biomass char oil component jointly.The method is implemented convenient, does not need to carry out large adjustment or variation to biomass pyrogenation gasification technique, does not need high-temperature area, only need to arrange a metal discharge region; Do not need to use catalyzer, avoid the problems such as catalyst deactivation.The Efficient Conversion of tar both can reduce or eliminate the problems such as equipment blocking that tar causes or corrosion, can also improve productive rate and the quality of biogas, improve energy utilization efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the simulator strengthening coke tar cracking in gasifying biomass pyrolytic process;
Fig. 2 is microwave metal discharge lysed biomass tar process flow sheet of the present invention.
Wherein, 1-gas cylinder, 2-glass rotameter, 3-laboratory push-and-pull syringe pump, 4-XYE digital display constant temperature electric heating cover, 5-Glanz household microwave oven, 6-quartz reactor, 7-T-valve, 8-Fourier infrared spectrograph, 9-Clarus500GC gas chromatograph.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described.
Embodiment 1
As Fig. 1, shown in 2, the simulator of coke tar cracking is strengthened in a kind of gasifying biomass pyrolytic process, by gas cylinder 1, laboratory push-and-pull syringe pump 3, XYE digital display constant temperature electric heating cover 4, Glanz household microwave oven 5, quartz reactor composition 6 is connected in turn by silicone tube, gas cylinder 1 and XYE digital display constant temperature electric heating arrange glass rotameter 2 between overlapping 1, laboratory push-and-pull syringe pump 3 overlaps 4 by silicone tube with XYE digital display constant temperature electric heating and is connected, quartz reactor 6 is positioned in Glanz household microwave oven 5, the position of the inlet pipe of quartz reactor 6 is higher than escape pipe, the escape pipe of quartz reactor 6 is connected with Fourier infrared spectrograph 8 and Clarus500GC gas chromatograph 9 by T-valve 7.The circular glass cotton that clip is identical with quartz reactor 6 bore is layered on bottom quartz reactor 6.Take quartz sand according to quartz reactor 6 size, be laid on the glass wool bottom quartz reactor 6.For playing the effect of protection quartz reactor 6 and insulation, the amount of quartz sand is moderate, and accumulation of heat is limited very little, gas heat absorption superdistension, then occupies the too many volume of reactor too much, have compressed the amount of reactant gases.
The stainless steel metal bar intercepting certain length according to requirement of experiment is several, and by certain arrangement mode, (metal strip is in the reactor generally in M shape
arrangement) smooth put on the quartz sand of quartz reactor 6, and with flange, quartz reactor 6 is fixed.In order to evade the uncertain factor in experimentation, and it is all consistent as much as possible to make often to organize experiment other reaction conditionss except investigating object, and ensures that quartz reactor 6 is placed on the same position in Glanz household microwave oven 5.
Open carrier gas gas circuit by air pressure adjustment to 0.2MPa, glass rotameter 2 is adjusted to 1000ml/min.Check the resistance to air loss of pipeline, confirm the air starting after resistance to air loss well to discharge in reactor, and keep this state to purge 30min with the intrasystem air of emptying.Open XYE digital display constant temperature electric heating cover 4 while purging air, temperature is adjusted to 200 DEG C, waiting temperature rises.Purging terminates the gas collection bag that rear use volume is 1L and collects one bag of gas in order to follow-up test analysis use.
Toluene being injected path is connected on reactive system, injects toluene by predetermined amount of flow.When toluene is passed in quartz reactor 6, open Glanz household microwave oven 5 switch and carry out catalytic cracking reaction.Each experiment all ensures the Zhong Xin Wei Jia of reactor in Glanz household microwave oven 5, and highly certain.Use T-valve 7 to be arranged on the outlet of reactant gases, one end uses the gas collection bag that volume is 3L to collect product gas, and an end is received Fourier infrared spectrograph 8 and carried out gas on-line checkingi.
Question response terminates rear closedown Glanz household microwave oven 5, detects by the gaseous constituent of gas chromatograph 9 pairs of gained.No longer have a discharging condition with metal strip, in quartz reactor 6, there is no the mark that electric discharge phenomena occur as reaction end.Through lot of experiment validation, when ensureing that reaction conditions (microwave power, discharge metal quantity and arrangement position, reactor putting position etc.) is consistent, although metal discharge still time point that is unstable, electric discharge is uncertain, discharge time total in whole process and intensity are much the same.
Scission reaction starts that the cleavage rate of rear toluene is the highest can reach 100%, split product composition mainly H
2, C
2h
2, CH
4deng.
Embodiment 2
In biomass pyrogenation gasification gas simulator, using toluene as modelling tar product, with N
2as carrier gas, N
2flow is 1000ml/min, and toluene input is 1ml/min, and the heating evaporation temperature of toluene is 200 DEG C.At microwave field metal discharge conversion zone, the microwave field environment of constant power 700W is set, (such as 8 strip metal materials) Ni of number stronger for degree of discharge is placed in microwave field to produce the reaction of microwave metal discharge.Make the metal discharge district of tar modelling thing toluene vapor by building, obtaining product main component to split product collection by GC detection is H
2and N
2, wherein H
2account for 4%.
Embodiment 3
In biomass pyrogenation gasification gas simulator, using toluene as modelling tar product, with N
2as carrier gas, N
2flow is 1000ml/min, and toluene input is 1ml/min, and the heating evaporation temperature of toluene is 200 DEG C.At microwave field metal discharge conversion zone, the microwave field environment of constant power 700W is set, (such as 3 strip metal materials) Ni of number more weak for degree of discharge is placed in microwave field to produce the reaction of microwave metal discharge.Make the metal discharge district of tar modelling thing toluene vapor by building, obtaining product main component to split product collection by GC detection is H
2and N
2, wherein H
2account for 1.2%.
In the identical situation of other experiment conditions of guarantee, use one species metal strip, the number only changing metal strip is tested.Found that, the quantity of same metal is more, and electric discharge phenomena are more obvious.In the detection of splitting gas composition, H
2content the highest.And C
2h
2, CO, CH
4content then relatively less.Therefore H is used
2content characterize the cracking degree of toluene, find that amount of metal is more, cracking degree is stronger.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. in a gasifying biomass pyrolytic process, strengthen the device of coke tar cracking, it is characterized in that, by microwave generating apparatus and excite electric discharge device to form, the microwave that described microwave generating apparatus produces excites electric discharge device by waveguide input, described exciting in electric discharge device has transiting state metal or its alloy or its Nano/micron state particle, on the described flue exciting electric discharge device to be arranged on gasifying biomass pyrolysis installation, temperature is the region of 200 DEG C-800 DEG C, described in excite electric discharge device to be made up of non-absorbing material.
2. device as claimed in claim 1, it is characterized in that, described transiting state metal is Fe, Ni, Co, Cu.
3. device as claimed in claim 1, it is characterized in that, described metal form is strip, spination, spherical, needle-like, prickle shape or Nano/micron Granular composite be carried on medium, described medium is microwave transparency high temperature material.
4. device as claimed in claim 1, is characterized in that, described in excite in electric discharge device and also arrange loading type iron sill, carried copper-base, activated carbon or activated coke.
5. device as claimed in claim 1, it is characterized in that, described non-absorbing material is quartzy class, corundum class material.
6. in a gasifying biomass pyrolytic process, strengthen the simulator of coke tar cracking, it is characterized in that, by gas cylinder, laboratory push-and-pull syringe pump, digital display constant temperature electric heating cover, microwave oven, quartz reactor forms, described gas cylinder, digital display constant temperature electric heating cover, quartz reactor is connected in turn by pipeline, described digital display constant temperature electric heating cover is connected with laboratory push-and-pull syringe pump, described quartz reactor is arranged in described microwave oven, the glass wool of the shape identical with its bore is covered with bottom described quartz reactor, described glass wool tiles one deck quartz sand, described quartz reactor flange is fixed.
7. device as claimed in claim 6, is characterized in that, the pipeline between described gas cylinder and digital display constant temperature electric heating overlap arranges glass rotameter.
8. device as claimed in claim 6, it is characterized in that, described pipeline is silicone tube.
9. device as claimed in claim 6, it is characterized in that, in described quartz reactor, reacted gas is connected with gas chromatograph with infrared spectrometer respectively by the threeway on pipeline.
10. in a gasifying biomass pyrolytic process, strengthen the method for coke tar cracking, it is characterized in that, the section of flue-gas temperature 200 DEG C-800 DEG C in biomass pyrogenation gasification device, the electric discharge phenomena strengthening coke tar cracking utilizing microwave field and metal interaction to produce, described microwave frequency is 2450MHz or 915MHz.
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Cited By (9)
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| CN105861006A (en) * | 2016-06-17 | 2016-08-17 | 安徽新生力生物科技有限公司 | Biomass pressurized-pyrolysis technology based on high-voltage electrolysis |
| CN108439377A (en) * | 2018-05-18 | 2018-08-24 | 浙江大学 | It is a kind of to cooperate with processing organic liquid waste using non-thermal plasma trap and prepare the device and method of graphene |
| CN108745362A (en) * | 2018-06-26 | 2018-11-06 | 山东科技大学 | The preparation method and application of the microwave discharge metallic catalyst of feature carbon film coated |
| CN109647306A (en) * | 2019-01-14 | 2019-04-19 | 山东大学 | A kind of microwave is according to the device and method for decomposing liquid chemical weapons under spoke |
| CN109821372A (en) * | 2019-02-21 | 2019-05-31 | 东华大学 | A kind of microwave induced metal discharge carries out the device and method of denitrating flue gas |
| CN112662413A (en) * | 2020-12-22 | 2021-04-16 | 华中科技大学 | Device and method for high-value utilization of biomass based on photo-thermal coupling |
| CN114101297A (en) * | 2021-11-19 | 2022-03-01 | 天津商业大学 | Device and method for treating photocuring waste through ultraviolet-assisted pyrolysis |
| CN114603484A (en) * | 2022-03-08 | 2022-06-10 | 湖南科技大学 | Metal bond grinding wheel microwave direct finishing method and system |
| CN114603485A (en) * | 2022-03-08 | 2022-06-10 | 湖南科技大学 | Metal bond grinding wheel microwave direct dressing method and device |
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| CN108745362A (en) * | 2018-06-26 | 2018-11-06 | 山东科技大学 | The preparation method and application of the microwave discharge metallic catalyst of feature carbon film coated |
| CN108745362B (en) * | 2018-06-26 | 2021-11-26 | 山东科技大学 | Preparation method and application of microwave discharge metal catalyst coated by characteristic carbon film |
| CN109647306A (en) * | 2019-01-14 | 2019-04-19 | 山东大学 | A kind of microwave is according to the device and method for decomposing liquid chemical weapons under spoke |
| CN109821372A (en) * | 2019-02-21 | 2019-05-31 | 东华大学 | A kind of microwave induced metal discharge carries out the device and method of denitrating flue gas |
| CN112662413A (en) * | 2020-12-22 | 2021-04-16 | 华中科技大学 | Device and method for high-value utilization of biomass based on photo-thermal coupling |
| CN114101297A (en) * | 2021-11-19 | 2022-03-01 | 天津商业大学 | Device and method for treating photocuring waste through ultraviolet-assisted pyrolysis |
| CN114603484A (en) * | 2022-03-08 | 2022-06-10 | 湖南科技大学 | Metal bond grinding wheel microwave direct finishing method and system |
| CN114603485A (en) * | 2022-03-08 | 2022-06-10 | 湖南科技大学 | Metal bond grinding wheel microwave direct dressing method and device |
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