CN105623687B - A kind of fuse salt spray pyrolysis biomass joint prepares bio oil and the apparatus and method of multiporous biological charcoal - Google Patents
A kind of fuse salt spray pyrolysis biomass joint prepares bio oil and the apparatus and method of multiporous biological charcoal Download PDFInfo
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- CN105623687B CN105623687B CN201610119442.7A CN201610119442A CN105623687B CN 105623687 B CN105623687 B CN 105623687B CN 201610119442 A CN201610119442 A CN 201610119442A CN 105623687 B CN105623687 B CN 105623687B
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- spray pyrolysis
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- 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
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- 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
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
- C10B49/14—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot liquids, e.g. molten metals
-
- 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
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
-
- 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
Abstract
The present invention relates to biomass resource utilization field, there is provided a kind of fuse salt spray pyrolysis biomass joint prepares bio oil and the apparatus and method of multiporous biological charcoal.Using the fuse salt with high accumulation of heat-heat transmission function as heat carrier, fuse salt is fully contacted with biomass in a manner of spray and realize fast pyrogenation, fused salt ion form biomass pyrolysis provides homogeneous catalysis or Control of chemical reaction.Fuse salt can storage reaction process liberated heat, serve as the effect of reaction medium, chemical heat is rationally utilized with outside heat.Pyrolytic carbon persistently permeates and washed away through fused salt, removes the tar being blocked in charcoal space so that the void open of pyrolytic carbon and unimpeded, multiporous biological carbon of the formation with certain adsorption capacity.The present invention is using double fused salt spray pyrolysis systems.This method technological process is short, easy to operate, and raw material is sent into or removed by being pyrolyzed basket, and pyrolytic carbon separates simply with fused salt, final to realize that pyrolysis biomass joint prepares bio oil and charcoal.
Description
Technical field
The present invention relates to biomass resource utilization field, and in particular to fuse salt spray pyrolysis biomass joint prepares biology
The apparatus and method of oil and charcoal.
Background technology
With traditional fossil energy increasingly depleted, and the environmental pollution due to being brought using fossil energy is increasingly tight
Weight, biomass energy is as a kind of low-sulfur, the cleaning of low nitrogen and carbon dioxide " zero-emission " and regenerative resource, while biomass
Aboundresources, gradually receive the concern and attention of domestic and international researcher.
Biomass pyrolytic is a kind of high efficiency technical of conversion of biomass to pyrolysis oil, solid carbon and combustible gas.Pyrolysis installation
Energy-conservation be essential, at present, biomass pyrolytic technology is straight using reactor indirectly heat and solid/gas heat-carrying
Connect heating pyrolytic process.Indirectly heat heat transfer rate is slow, and heat transfer efficiency is low；Gas heat-carrying shortcoming is to need a large amount of high warm cigarettes
Gas high energy consumption；Thermoset carrier is mainly quartz sand carrier, and conventional pyrolysis installation is recirculating fluidized bed, realizes the fast speed heat of biology
Solution.Recirculating fluidized bed has the advantages of thermal efficiency is high, but needs the use of carrier gas and the power consumption of follow-up gas solid separation big.Simultaneously
Pyrolysis bio-oils have penetrating odor, and density is higher, and acid stronger, oxygen content is higher and calorific value is relatively low and composition is very multiple
Miscellaneous, bio oil is difficult to directly utilize, and oil quality needs to improve.Catalysis pyrolysis improves oil quality, but catalyst preparation to a certain degree
And Catalysts Deactivation Problems cause pyrolysis operating cost to increase.
Fuse salt has good heat storage capacity, and mass-and heat-transfer coefficient is high, and viscosity is low, volatility is low and suitable fusing point
The physical characteristics such as temperature.Molten salt system can provide a liquid phase environment for biomass, and heat transfer and mass transfer are highly uniform and rapid, energy
Enough rapidly and efficiently decomposing biomass, can be used for the technical process of biomass fast pyrolysis.Fused salt ion is present simultaneously, makes a living
Material pyrolysis provides homogeneous catalysis or Control of chemical reaction, and pyrolysis gas of biomass is reformed through molten salt layer ionic catalysis, is biomass
Thermal decomposition product directed chemical composition provides possibility.Because biomass density is low so that biomass is difficult to soak in fused salt liquid levels layer
Bubble and fully contact, while a large amount of gas explosion bubblings in biomass pyrolysis process, form pressure and cause pyrolysis gas to drive molten salt layer liquid
Face is splashed, and causes fused salt pyrolytic process to be difficult to control, while pyrolytic carbon is formed in pyrolytic process and is remained in fuse salt, due to molten
Saline solution bread wraps up in charcoal so that charcoal is difficult to burn in fused salt, and charcoal separates with fused salt to be limited to biomass thermal management application.
The content of the invention
The present invention makes full use of the advantages of fuse salt heat treatment method, faces and asks for fuse salt pyrolysis biomass technique
Topic.A kind of high-temperature fusion salt spray pyrolysis biomass multi-production of the present invention prepares device and the side of bio oil and multiporous biological charcoal
Method.
Technical scheme：
A kind of fuse salt spray pyrolysis biomass joint prepares the device of bio oil and multiporous biological charcoal, and the device includes two
Set device for transporting objects, two sets of spray pyrolysis devices, cyclone hydraulic separators, solid residue collect outlet, fused salt heating bath, RY types melt
Salt circulating pump, condenser, liquid header and gas collector；Device for transporting objects is connected with spray pyrolysis device forms fused salt
Spray pyrolysis biomass system of subject, whole device use cube chamber structure；Two sets of device for transporting objects and two sets of spray pyrolysis
Device cooperating；
Device for transporting objects is conveyed using line thread step-by-step system, and device for transporting objects upper end is charging aperture, inside it
Provided with cube material basket, material basket bottom is loose structure, and aperture is less than 0.5mm, and material basket is connected with screw thread transmission pole, and leads to
Cross the control of straight line screw mandrel stepper；Material basket supporting bracket is provided with inside device for transporting objects, for supporting material basket；Material conveys
Device is contacted with spray pyrolysis device using material disengaging sealing neck, is realized between device for transporting objects and spray pyrolysis device
Sealing communicates；
Spray pyrolysis device includes fused salt spray head, micro porous filtration baffle plate and sludge outlet, and spray pyrolysis device outer layer is adopted
Coated with warming plate, form heat-insulation layer；Spray pyrolysis device inner upper end is provided with fused salt spray head, subordinate in spray pyrolysis device
End is provided with micro porous filtration baffle plate, and aperture is less than 100 mesh；Spray pyrolysis device lower end outside is provided with sludge outlet；Spray pyrolysis fills
Bottom set portion is connected with cyclone hydraulic separators, avoids fused salt from being condensed in cyclone hydraulic separators, and cyclone hydraulic separators outer wall is auxiliary using resistance wire
Help heating；Cyclone hydraulic separators is provided with solid residue and collects outlet, and cyclone hydraulic separators passes sequentially through fused salt heating bath and RY types melt
Salt circulating pump is back to spray pyrolysis device, is recycled by fused salt spray head；Pyrolysis gas outlet is arranged on spray pyrolysis dress
Top set portion, condensed device condense collecting biological oil, can not cool solidifying combustible gas enter gas collector or burn heat is provided；Outside it
Portion is connected by fused salt heating bath with adjustable speed RY type molten salt circulating pumps, prevents that fuse salt is anti-in spray pyrolysis device with biomass
Seasonable solidification, residence time of the fuse salt in spray pyrolysis device are not less than 5s；
Molten salt pool valve I, RY types molten salt circulating pump and No. 1 spray are provided between fused salt heating bath and RY type molten salt circulating pumps
Molten salt pool valve II is provided between pyrolysis installation, molten salt pool valve is provided between RY types molten salt circulating pump and No. 2 spray pyrolysis devices
Door III.
A kind of fuse salt spray pyrolysis biomass joint prepares bio oil and the method for multiporous biological charcoal, and step is as follows：It is raw
Material grainses are packed into the material basket in device for transporting objects via charging aperture, and material basket is defeated through screw thread by straight line screw mandrel stepper
Send bar to be delivered in spray pyrolysis device, and there is material disengaging sealing neck to realize between spray pyrolysis device and device for transporting objects
Sealing, while use N2Or the air in vacuum filtration 5-10min discharge spray pyrolysis devices；
Molten salt pool valve I, molten salt pool valve II and RY type molten salt circulating pumps are opened, high-temperature fusion salt is via fused salt spray head
Contacted with biological particles and produce pyrolysis gas, pyrolysis oil is collected in condensed device condensation, and condensible gas does not enter after sampling analysis
Enter gas collector or be passed through incinerator and burning offer additional energy is provided；As fused salt persistently permeates biological particles, the bottom of through
Micro porous filtration baffle plate in portion's flows into cyclone hydraulic separators filtering solid residue, flows into fused salt heating bath circulating-heating；Treat biological particles
Completely after pyrolysis, molten salt pool valve II is closed, material basket removes spray heat by straight line screw mandrel stepper through screw thread transmission pole again
Collect pyrolytic carbon after solution device cooling, and prepare next batch material pyrolysis charring, while open molten salt pool valve III, repeat with
Upper step opens No. 2 fused salt spray pyrolysis devices, double spray pyrolysis devices alternate run successively；A small amount of micro-solid residue point
Outlet discharge is not collected via the solid filter residue of spray pyrolysis bottom of device sludge outlet and suspension separator.
The present invention can choose metal, the chlorate of alkali metal, silicate, nitrate, phosphate or a variety of above-mentioned compositions
Eutectic mixture.To ensure that fused salt circulates the continuity of pyrolysis system, the present apparatus sprays system of subject using double fused salts and criticized
Secondary independent operating mode.
The operation principle of the present invention：
Material basket endogenous substance contacts with the fuse salt sprayed and the fast decoupled that is heated forms pyrolysis gas and pyrolytic carbon；Pyrolysis
Gas is collected into the pyrolysis oil of high-quality wearing from fuse salt liquid levels layer after the catalysis of molten metal salt ion through gas outlet condensation, no
Condensable fuel gas heats through incinerator for melting；As fused salt persistently sprays, fused salt persistently infiltrates through life through being pyrolyzed layer of charcoal
Material pyrolysis is progressively pyrolyzed lower floor's biomass, until biomass is pyrolyzed completely；Fuse salt flows out through material basket base apertures and through protecting
Warm solution orlop cyclone hydraulic separators, the fuse salt through separating solid residue after-purification flow into molten salt pool through melting salt pond reheating
Recycle, molten pyrolysis obtains multiporous biological charcoal and is sent into through discharging opening output device in porous carbon collection device.
Beneficial effect of the present invention：
(1) device uses the fuse salt with accumulation of heat-heat transmission function abundant with biomass as heat carrier, fuse salt
Fast pyrogenation is realized in contact, improves mass transfer and heat transfer efficiency, at the same fuse salt can storage reaction process liberated heat, serve as
The effect of reaction medium, chemical heat is set rationally to be utilized with outside heat；
(2) fuse salt fountain pyrolysis biomass is one big characteristic of this method, and the arrangement achieves biomass and fuse salt
Fully contact, avoids pyrolysis gas from causing fused salt to splash a large amount of bubblings of liquid levels layer；
(3) fused salt ion is present, and form biomass pyrolysis provides homogeneous catalysis or Control of chemical reaction, realizes that biomass is quick
Catalysis pyrolysis；
(4) pyrolytic carbon persistently permeates and washed away through fused salt, removes the tar being blocked in charcoal space so that pyrolytic carbon
Void open and unimpeded, multiporous biological carbon of the formation with certain adsorption capacity；
(5) repacking is put simple in construction and compact, and pyrolytic carbon separates simply with fused salt, final to realize pyrolysis biomass joint system
Standby bio oil and multiporous biological charcoal.
Brief description of the drawings
Accompanying drawing is that fuse salt spray pyrolysis biomass joint prepares bio oil and the schematic device of multiporous biological charcoal.
In figure：1 charging aperture；2 straight line screw mandrel steppers；3 material basket supporting brackets；4 screw thread transmission poles；The disengaging sealing of 5 materials
Neck；6 material baskets；7 fused salt spray heads；8 micro porous filtration baffle plates；9 sludge outlets；10 warming plates；11 cyclone hydraulic separators；12 solids
Residue collects outlet；13 fused salt heating baths；14RY type molten salt circulating pumps；15 condensers；16 liquid headers；17 gas collections
Device.
Embodiment
Below in conjunction with accompanying drawing and technical scheme, embodiment of the invention is further illustrated.
ZnCl2- KCl mixed meltings salt pyrolysis corn cob granule prepares bio oil and multiporous biological charcoal
Choose the zinc chloride with catalysis and activation and form low temperature molten salt with potassium chloride (mol ratio 7/6),
The fused salt fusing point is low, keeps fine stability at 200~500 DEG C, meets biomass fast pyrogenation temperature.Control molten salt pool temperature
For 500 DEG C, line temperature is controlled at 450 DEG C.10g particle diameters are weighed to be walked by line thread through material basket for 1-3mm corn cob granules
Enter mode and convey to deliver in No. 1 spray pyrolysis device, protected using flow velocity 100ml/min high-purity N 2 (99.99%) purging pyrolysis
After warm storehouse 10min.Close N2 and open molten salt pool valve I and II and RY type molten salt circulating pumps, control fused salt flow velocity 20g/ simultaneously
Min, reaction time 30min, it is rear to close valve II, No. 2 spray pyrolysis devices are opened, are repeated the above steps.Reaction terminates, and receives
Collection and weighing condensate liquid, pyrolytic carbon is after washing in 105 DEG C of baking ovens.
Wall temperature reaches 450 DEG C after 1min in spray pyrolysis device, and liquid phase yield is 25-35wt%, solid 45%.Liquid
Phase product water content is 60%, is formed with water and is well mixed liquid phase, minimal amount of water-insoluble tar, the GC/MS analyses of product
As a result it is：Aldehydes and flavonoid content height account for 41.61% and 31.15% respectively, are secondly phenols 28.98% and a small amount of acid and ester
Class compound.Fused salt aggravation biomass fast pyrogenation is verified, obtains a large amount of lightweight oil ingredients.Pyrolysis gas main component is CO2、
CO、CH4、H2And a small amount of C2-C4Olefin gas.C element content is up to 87% or so in pyrolytic carbon, specific surface area 300-
380m2/g。
Claims (2)
1. a kind of fuse salt spray pyrolysis biomass joint prepares the device of bio oil and multiporous biological charcoal, it is characterised in that should
Device adds including two sets of device for transporting objects, two sets of spray pyrolysis devices, cyclone hydraulic separators, solid residue collection outlet, fused salt
Hot pond, RY types molten salt circulating pump, condenser, liquid header and gas collector；Device for transporting objects and spray pyrolysis device
It is connected and forms fused salt spray pyrolysis biomass system of subject, whole device uses cube chamber structure；Two sets of device for transporting objects and
Two sets of spray pyrolysis devices replace cooperating；
Device for transporting objects is conveyed using line thread step-by-step system, and device for transporting objects upper end is charging aperture, is internally provided with
Cube material basket, material basket bottom are loose structure, and aperture is less than 0.5mm, and material basket is connected with screw thread transmission pole, and by straight
Filament bar stepper controls；Material basket supporting bracket is provided with inside device for transporting objects, for supporting material basket；Device for transporting objects
Contacted with spray pyrolysis device using material disengaging sealing neck, realize and sealed between device for transporting objects and spray pyrolysis device
Communicate；
Spray pyrolysis device includes fused salt spray head, micro porous filtration baffle plate and sludge outlet, and spray pyrolysis device outer layer is using guarantor
Warm plate cladding, forms heat-insulation layer；Spray pyrolysis device inner upper end is provided with fused salt spray head, and spray pyrolysis device interior lower end is set
There is micro porous filtration baffle plate, aperture is less than 100 mesh；Spray pyrolysis device lower end outside is provided with sludge outlet；Spray pyrolysis device bottom
Portion is connected with cyclone hydraulic separators, avoids fused salt from being condensed in cyclone hydraulic separators, and cyclone hydraulic separators outer wall is added using resistance wire auxiliary
Heat；Cyclone hydraulic separators is provided with solid residue and collects outlet, and cyclone hydraulic separators passes sequentially through fused salt heating bath and RY type fused salts follow
Ring blowback flow to spray pyrolysis device, is recycled by fused salt spray head；Pyrolysis gas outlet is arranged on spray pyrolysis device top
Portion, condensed device condense collecting biological oil, can not cool solidifying combustible gas enter gas collector or burn heat is provided；It is outside logical
Cross fused salt heating bath with adjustable speed RY type molten salt circulating pumps to be connected, prevent fuse salt with biomass in spray pyrolysis device reaction
Solidification, residence time of the fuse salt in spray pyrolysis device are not less than 5s；
Molten salt pool valve (I), RY types molten salt circulating pump and No. 1 spray heat are provided between fused salt heating bath and RY type molten salt circulating pumps
Molten salt pool valve (II) is provided between solution device, molten salt pool valve is provided between RY types molten salt circulating pump and No. 2 spray pyrolysis devices
Door (III).
2. a kind of fuse salt spray pyrolysis biomass joint prepares bio oil and the method for multiporous biological charcoal, it is characterised in that step
It is rapid as follows：Biological particles are packed into the material basket in No. 1 device for transporting objects via charging aperture, and material basket is walked by straight line screw mandrel
Enter machine to be delivered in No. 1 spray pyrolysis device through screw thread conveying lever, and there is material disengaging sealing neck to realize No. 1 spray pyrolysis dress
The sealing between No. 1 device for transporting objects is put, while uses N2Or vacuum filtration 5-10min is discharged in No. 1 spray pyrolysis device
Air；
Molten salt pool valve (I), molten salt pool valve (II) and RY type molten salt circulating pumps are opened, high-temperature fusion salt is via fused salt spray head
Contacted with biological particles and produce pyrolysis gas, pyrolysis oil is collected in condensed device condensation, and condensible gas does not enter after sampling analysis
Enter gas collector or be passed through incinerator and burning offer additional energy is provided；As fused salt persistently permeates biological particles, the bottom of through
Micro porous filtration baffle plate in portion's flows into cyclone hydraulic separators filtering solid residue, flows into fused salt heating bath circulating-heating；Treat biological particles
Completely after pyrolysis, molten salt pool valve (II) is closed, material basket removes No. 1 spray by straight line screw mandrel stepper through screw thread transmission pole again
Pyrolytic carbon is collected after leaching pyrolysis installation cooling, and prepares next batch material pyrolysis charring, while opens molten salt pool valve (III),
Repeat above step and open No. 2 fused salt spray pyrolysis devices, double spray pyrolysis devices alternate run successively；A small amount of micro-solid
Residue collects outlet discharge via the solid filter residue of spray pyrolysis bottom of device sludge outlet and suspension separator respectively.
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| CN106955668A (en) * | 2017-04-01 | 2017-07-18 | 东北农业大学 | A kind of method that fuse salt assisted with high-temperature charring prepares N doping multiporous biological charcoal |
| CN106938190A (en) * | 2017-04-19 | 2017-07-11 | 东北农业大学 | A kind of preparation method of the lamella multiporous biological charcoal with strong adsorption function |
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| CN109609151B (en) * | 2018-11-28 | 2021-01-05 | 大连理工大学 | Device and method for preparing ordered mesoporous carbon-metal composite material from solid waste biomass |
| CN109847657B (en) * | 2019-01-22 | 2020-08-14 | 华中科技大学 | Fused salt heat supply fluidized bed pyrolysis reaction furnace and reaction method |
| CN110184094A (en) * | 2019-06-20 | 2019-08-30 | 浙江工业大学 | A kind of fused salt removes the method and device of tar in pyrolysis gas of biomass |
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| CN110776958B (en) * | 2019-11-20 | 2021-04-02 | 刘民凯 | Low-rank coal partition pyrolysis gasification multi-combined supply system and method based on molten bath bed |
| CN111186839B (en) * | 2020-02-27 | 2021-11-16 | 中国科学院化学研究所 | Reaction system and method for preparing nano-pore carbon material by using ternary low-temperature molten salt |
| CN112920860A (en) * | 2021-01-21 | 2021-06-08 | 东南大学 | Device for co-producing carbon-containing precursor and high-quality oxygen-containing fuel on line by using biomass pyrolysis gas |
| CN114717015B (en) * | 2022-04-05 | 2023-10-24 | 昆明理工大学 | Method and device for co-producing fuel gas by using organic waste and molten salt to prepare carbon-based material |
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