CN1962818B - Process for preparing bio-oil by using rapid thermal cleavage technology - Google Patents
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Abstract
The invention discloses an oil making method through rapid heat cracking, which comprises the following steps: drying and grinding the raw materials; transmitting the disposed materials into rector to crack; separating the product to obtain the biological oil.
Description
Technical field
The present invention relates to a kind of method of producing bio-oil, particularly relate to a kind of fast pyrolysis technology of utilizing and per hour handle 500 kilograms of powdered rice hulls, the method for one ton of bio-oil of daily output.
Background technology
The energy is that human society exists one of important substance basis with development.In more than 200 year of past, the energy mainly relies on the energy system based on coal, oil, Sweet natural gas.Yet above these resources are exhausted day by day and environment constantly worsens, and brought serious consequence to the earth, and threatened human existence and development.Step into today of 21 century, concern the energy problem of the national security and the sustainable development of socio-economy, become the central topic that various countries, the world today are faced.
Biomass energy is as the fourth-largest Energy resources in the consumption of world's primary energy source, and it is closely bound up with the human lives in historical long river, is the renewable energy source that can store and transport, also will occupy critical role in the human following energy resource system.
Bioenergy is meant the various organisms that form by photosynthesis, comprises all animals and plants and microorganism.To be sun power be stored in form of energy in the biomass with the chemical energy form to biomass energy, is the energy of carrier with biomass, can be converted into conventional solid-state, gaseous state and liquid fuel.It is inexhaustible, nexhaustible a kind of renewable new forms of energy.From the broad sense opinion, biomass energy should belong to a kind of manifestation of sun power.
The technological approaches of biomass energy trans-utilization mainly comprises burning, thermochemical method, biochemical process, chemical method and physico-chemical processes etc.The flow process of the technology of domestic and international existing biomass energy trans-utilization as shown in Figure 1.
China is that populous agricultural is national, and biomass energy is occupied considerable status in the energy structure of China, and especially in vast Rural areas, biomass energy once was the most important energy.But for a long time, the utilization of biomass energy is based on direct burning mostly, and not only thermo-efficiency is low, and is accompanied by the discharging of a large amount of flue dust and surplus ash, becomes one of important factor that hinders rural economy and social progress.Along with science and technology development and progress, biomass energy can be used efficiently by various switch technologies, produces various clean fuels and electric power, to substitute mineral fuel such as coal, oil and natural gas.So, develop and use biomass energy, to realizing Sustainable development, ensure national energy security, improve living environment and reducing the discharging carbonic acid gas, all have vital role and practical significance.
Comparatively near the Rural areas in commercial energy resource producing region or rich Rural areas, commercial energy resource (coal, liquefied gas) has become its main cooking and life with can, the incendiary stalk at first becomes replaced object in a conventional manner, causes the stalk amount of discarded field to increase year by year.The phenomenon of the discarded stalk of many area burnings has continued for many years, remains incessant after repeated prohibition, and has caused serious topsoil.Particularly, make the air quality severe exacerbation, the accident that aviation socked-in and motorway knock into the back and collide has repeatedly taken place, become a serious social concern of governments at all levels' concern in harvest season concentrated combustion discharging.Along with the raising of China rural area modernization level from now on, the situation of this waste and pollution will be more and more serious.So utilize biomass switch technology efficiently, the depleted biomass resource is converted to high-grade fuel oil, combustion gas and electric energy, not only can improves agriculture output, increase farmers' income, alleviate peasant's labour intensity, can reduce pollution again, promote ecological benign cycle.
Some are also disclosed in the prior art about preparing the method for bio-oil.Carry according to document, set up the experimental installation of different cleavage methods in the U.S., the capacity of per hour producing is from tens to the hundreds of kilogram, the highest oil yield rate about 70%.Italy also sets up the device of 500kg/h.Canada has developed the kinds of processes experiment, and big experimental installation is arranged, day working ability 200T.Some countries of China and USA and Europe compare, and slower to this technical study starting, over past ten years, the breadboard work of some this respects has been done by units such as Shenyang agricultural university, Zhejiang University, the Chinese Academy of Sciences and Shandong Technology Univ, does not see the report that new development is arranged recently.
But there are some places that have much room for improvement in these methods, and such as the adaptability and the oil yield rate that improve raw material, reduce the coking phenomenon in the reactor, and continual and steady feeding or the like.
Summary of the invention
Main purpose of the present invention is, overcome the defective that the existing method of producing bio-oil exists, and provide a kind of method of new preparing bio-oil by using rapid thermal cleavage technology, technical problem to be solved provides a kind of feed system of automatic control, the assurance scission reaction is carried out under anaerobic state, thereby is suitable for practicality more.
Another object of the present invention is to, a kind of condensation method that uses in the method for preparing bio-oil by using rapid thermal cleavage technology is provided.
An also purpose of the present invention is, a kind of raw material widely that is suitable for is provided, when reducing material cost, improve the productive rate of biomass fuel, and exploitation has bio-oil byproduct and the more economical converting apparatus efficiently and the technology of value simultaneously, thereby be suitable for practicality more, and have the utility value on the industry.
The object of the invention to solve the technical problems realizes by the following technical solutions.The method of a kind of preparing bio-oil by using rapid thermal cleavage technology that proposes according to the present invention, this method comprises carries out drying, pulverizing to material, material after will handling then is transported to by feed system and carries out heat scission reaction in the reactor, and the product that reaction obtains separated obtain described bio-oil, this method is further comprising the steps of: (a) at first under material and air state of contact, feed system with traditional screw propulsion method with mass transport in materials-stored box; (b) with the material of materials-stored box by gas delivery to being provided with the adding in the hopper of the transmitter of determining the material addition; (c) add transmitter in the hopper and determine that the accumulation degree of material reaches predetermined standard after, be arranged on the electronics open and close valve that adds on the hopper and close automatically and add the hopper top cover, make material be in anaerobic state; And the electronics open and close valve that (d) adds hopper is when closing, the electronics open and close valve of feed bin is opened and the starting impulse feeding machine, material is sucked feed bin by pipeline, open the electronics open and close valve that adds hopper when sensors command feed bin electronics open and close valve was closed when the accumulation degree was up to standard, corresponding material is transported in the pyrolysis reactor by air pulse.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
The method of aforesaid preparing bio-oil by using rapid thermal cleavage technology, the water content of wherein said dried material is not more than 10%, and the particle diameter of the material after the pulverizing is 1-1.5mm.
The method of aforesaid preparing bio-oil by using rapid thermal cleavage technology, the material residence time in reactor is 1-3 second.
The method of aforesaid preparing bio-oil by using rapid thermal cleavage technology, the top temperature of wherein said heat scission reaction is 650 ℃, and carry out stage by stage according to following program: the fs carries out under 120 ℃-150 ℃, subordinate phase is carried out under 150 ℃-280 ℃, phase III carries out under 280 ℃-450 ℃, and the quadravalence section is carried out under 450 ℃-650 ℃.
The method of aforesaid preparing bio-oil by using rapid thermal cleavage technology, wherein this method comprises that also the solid product that will obtain in the pyrolysis reactor is transported in the fly-ash separator step of handling, obtain the solid product charcoal.
The method of aforesaid preparing bio-oil by using rapid thermal cleavage technology, wherein said fly-ash separator are cyclonic separator.
The method of aforesaid preparing bio-oil by using rapid thermal cleavage technology, wherein this method comprises also that the gaseous product that will obtain in the pyrolysis reactor is transported to and carries out condensation in the condenser system, collect the bio-oil that condensation obtains with biological oily holding tank then, and the not condensible gas part that will obtain sends into circulating air compressor and enters gas-holder, enters in the pyrolysis reactor as thermal source.
The condenser that comprises two connections in the condenser system wherein, the temperature of first condenser are 50 ℃-70 ℃, and the temperature of second condenser is-2 ℃-2 ℃.
The method of aforesaid preparing bio-oil by using rapid thermal cleavage technology, wherein said first condenser is striven gas in second at 1-2 usually and is chilled to below 350 ℃, the temperature of second condenser under refrigeration is about 0 ℃, vertically is provided with between first condenser and second condenser.
The present invention compared with prior art has tangible advantage and beneficial effect.By above technical scheme as can be known, in order to reach aforementioned goal of the invention, major technique of the present invention thes contents are as follows:
The present invention proposes a kind of method of preparing bio-oil by using rapid thermal cleavage technology, this technology is meant that biomass are under the condition of basic no oxygen (isolated with air), utilize the chemical bond in the heat energy cut-out biomass macromole, make it to change into the process of lower-molecular substance.Generate liquid bio oil, inflammable gas and solid biomass charcoal three portion of product by this thermochemistry switching process.The biomass through pyrolysis reaction primary process four-stage of can classifying:
1, drying stage: outer heat supply heated 120 ℃-150 ℃, makes that material evaporates moisture in the still.This stage material chemical composition is constant substantially.
2, the pre-charing stage (pre-thermo-cracking): heats up 150 ℃-280 ℃ the time, the material heat scission reaction is apparent in view, and chemical composition begins variation, and labile element (as hemicellulose) resolves into CO
2, material such as CO and little acetic acid.
3, the charing stage (solid decomposition): heat up 280 ℃-450 ℃ the time, material sharply decomposites a large amount of products, and discharges a large amount of reaction heat, is the thermopositive reaction stage.Generate in the product and contain acetic acid, wood tar oil and methyl alcohol (can separate out during cooling).Also has CO
2, CO, CH
4, H
2Deng gas.
4, calcination stage: the temperature range in this stage is 450 ℃-650 ℃.With the C-H in the figure body product, the further cracking of C-O key, remove the volatile matter that remains in the charcoal, thereby improve the quality of fixed carbon.
Above four-stage does not have obvious boundary to carry out continuously.
The main type of reactor that biomass fast pyrolysis uses has: entrained flow reactor, vacuum reactor, fixed-bed reactor, rotary kiln reactor (containing rotation awl, rotating screw reactor), ablation plate reactor, ablation Vortex reactor, liquefied bed reactor (containing the circulation liquefaction bed bioreactor).
To be temperature move with under interior, the condition of total pressure at 8kpa at 650 ℃ pyrolysis reactor among the present invention.
By technique scheme, the method for preparing bio-oil by using rapid thermal cleavage technology of the present invention has following advantage at least:
1, the technology of preparing bio-oil by using rapid thermal cleavage technology of the present invention is strong to the adaptive faculty of raw material; Thereby can reduce material cost.
2, the productive rate height (45%-70%) of the technology biomass fuel of preparing bio-oil by using rapid thermal cleavage technology of the present invention, and can develop simultaneously to have and be extensive use of the bio-oil byproduct that is worth, as the byproduct charcoal that obtains among the present invention, can be used as domestic fuel, smelt high-quality non-ferrous metal and cast iron fuel, do oozing the charcoal agent, can be made into graphite and gac of mechanical component; The not condensable gases that scission reaction produces also can be used as fuel.
3, the converting apparatus of the technology of preparing bio-oil by using rapid thermal cleavage technology of the present invention is compared with prior art with technology, and is efficient more economically.
4, the present invention adopts the secondary rapid condensation.Therefore avoid the macromole volatilization gas under comparatively high temps, further to be cracked into uncondensable micro-molecular gas, thereby improved the output of bio oil.
In sum, the method of the preparing bio-oil by using rapid thermal cleavage technology of special construction of the present invention, it has above-mentioned many advantages and practical value, have large improvement technically, and produced handy and practical effect, and the more existing method of producing bio-oil has the multinomial effect of enhancement, thereby be suitable for practicality more, and have the extensive utility value of industry.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.
The specific embodiment of the present invention is provided in detail by following examples and accompanying drawing thereof.
Description of drawings
Fig. 1 is the schematic flow sheet of the biomass energy trans-utilization of prior art.
Fig. 2 is the method synoptic diagram of preparing bio-oil by using rapid thermal cleavage technology of the present invention.
1: materials-stored box 2: add hopper 3: feed bin
4: electronics open and close valve 5: pressure pump 6: pyrolysis reactor
7: gas meter 8: gas tower 9: tornado dust collector
10: condenser 11: water-sealed tank 12: oil trap
13: storage tank 14: compressor 15: gas-holder
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, its concrete structure of method, feature and the effect thereof of the preparing bio-oil by using rapid thermal cleavage technology that foundation the present invention is proposed, describe in detail as after.
See also shown in Figure 2, the method of the preparing bio-oil by using rapid thermal cleavage technology of preferred embodiment of the present invention mainly comprises the following reaction member, promptly the materials-stored box shown in Fig. 21, add hopper 2, feed bin 3, electronics open and close valve 4, pressure pump 5, pyrolysis reactor 6, gas meter 7, gas tower 8, tornado dust collector 9, condenser 10, water-sealed tank 11, oil trap 12, storage tank 13, compressor 14 and gas-holder 15.
Idiographic flow is as follows.
At first adopt traditional spiral propeller that the material of 1-1.5mm particle diameter is sent into materials-stored box 1 mixing in the state mutually with air; Utilize the gas of thermo-cracking self generation by the feeding pressure pump, material in the materials-stored box 1 sent into air-flow add hopper 2, after transmitter was determined solid accumulation degree (predetermined standard) up to standard in the case, instruction electronics open and close valve 4 was closed the hopper top cover automatically, makes material be in anaerobic state; When adding hopper electronics open and close valve 4 and close, the electronics open and close valve 4 of feed bin 3 opens and the starting impulse feeding machine sucks material in the feed bin 3 by pipeline, and the electronics open and close valve 4 of sensors command feed bin 3 was closed when the accumulation degree was up to standard.Material is sent in the pyrolysis reactor 6 by air pulse.When feed bin 3 electronics open and close valves 4 are closed, add the electronics shut-off valve 4 of hopper 2 and open, so alternately move in succession, guaranteed the continuous production of single unit system.Material reacts in cracking reactor 6, and the gaseous product that obtains is transported in the gas tower 8 and cushions, and by tornado dust collector 9 solid product is separated then, and continues gaseous product is transported to and carry out condensation separation in the condenser 10.After the product that condensation separation obtains passed through separating of water-sealed tank 11 and oil trap 12, gas part (non-condensable gas) was input in the gas-holder 15 by compressor 14, and was transported in the cracking reactor 6 by gas meter 7 meterings; Liquid portion (being bio-oil) is transported in the storage tank 13 and stores.
Embodiment
The embodiment of present embodiment is as follows.The big 500kg/h of experimental scale (the material 500kg that per hour handles up, daily output bio-oil 1-2 ton).
(1) drying: too much moisture content is brought in the bio oil and goes in the material, must carry out drying to material, and it is 7.5KW mountain region board dryer that present embodiment adopts power of motor, per hour can dry material 700kg.Material after the oven dry requires water content to be not more than 8%.
(2) pulverize:, need material is pulverized for improving the output capacity of bio-oil.This is very necessary to improving heating rate.Because the particle diameter that material is enough little is one of essential condition of guaranteeing high heating rate.Present embodiment is material with the rice husk; Its particle diameter is 1-1.5mm.
(3) feeding.Convey materials is one of important technical links in the thermo-cracking flow process.Because biomass through pyrolysis is biomass (material) under the condition of anoxic or limited oxygen supply fully, the mass transport that particle diameter is very little is in the pyrolysis reactor.The method that combines with gas propulsive with screw propulsion is adopted in charging.
(4) heat scission reaction.The heat scission reaction temperature range is 120-650 ℃.Top temperature is 600-650 ℃.The gas phase residence time, heating rate can reach 2000k/s less than 3s.Another key of the technology of control thermo-cracking liquefaction is that very high heating rate and heat transfer rate will be arranged, the quick cooling of strict controlled temperature and thermo-cracking volatile matter.The not condensable gases that the present invention can utilize scission reaction to produce is made fuel.The thermo-cracking chamber temperature is in 120 ℃ of-150 ℃ of processes, mainly be material institute water content further to be evaporated take off its moisture content, temperature is in 150 ℃ of-280 ℃ of processes, and the apparent in view unsettled composition of material reaction begins to generate CO such as chemical compositions such as hemicelluloses
2, material such as CO and little acetic acid.Generally belong to the thermo-negative reaction stage through last.When temperature during at 280 ℃-450 ℃, material sharply carries out thermolysis, produces a large amount of degradation productions, and this solid decomposes (charing) stage and is generally the thermopositive reaction stage more than discharging a large amount of reaction heat.Temperature is by in 450 ℃ of-650 ℃ of processes, and C-H, C-O key are further cleaved, and generating product liquid has acetic acid, wood tar oil and methyl alcohol (separating out during cooling); CO is arranged in the gaseous product
2, CH
4, H
2Deng, flammable composition increases.More than do not have obvious boundary between several step of reaction, they are uninterruptedly to carry out continuously.
(5) gaseous product in the pyrolysis reactor enters the gas tower and enter the condensation program after the water spray is handled after the calcination.Solid product enters fly-ash separator from pyrolysis reactor, is preferably cyclonic separator and collects the charcoal product.
(6) condensation.Adopt the secondary rapid condensation.By two condensers that are connected, these two condensers are vertical through the oil vapour of water spray process and gaseous product, and condenser overhead is provided with cleaning plug mouth, and the bottom is provided with the bio oil holding tank.First condenser is reduced to gas temperature below 350 ℃; Second condenser uses greatly about 0 ℃ of cold water as cooling medium.Bio oil condensation and being collected in condenser, the gas of generation is by the vaporific tar of strainer filtering, and a part is sent into circulating air compressor and is entered gas-holder.Enter the combustion chamber of reactor as thermal source.
Test-results is as follows.
Mainly comprise bio-oil, charcoal, non-condensable gas in the reaction product.Existing division is as follows.
(1) be the experiment material with the rice husk, the oil yield rate of bio-oil is 45%.The bio-oil that obtains is the mixture of the high complicated organic composition of oxygen level, and it mainly comprises ether, ester, aldehyde, ketone, phenol, organic acid, alcohol.The rerum natura of bio-oil and composition data are as shown in table 1.
Table 1
| Physical properties | Representative value | Physical properties | Representative value |
| Water ratio/% | 15-30 | N | 0.1 |
| Physical properties | Representative value | Physical properties | Representative value |
| PH value | 2.5 | Ash | 0.1 |
| Relative density | 1.20 | Superior calorific value (changing) MJkg with water ratio -1 | 16-19 |
| Ultimate analysis/% | |||
| C | 56.4 | Viscosity (40 ℃, 25% water content)/cP | 40-100 |
| H | 6.2 | Solid impurity (charcoal) % | 1 |
| O | 37.3 | Vacuum distilling | The most degradation amount is 50% |
(2) charcoal
The charcoal that obtains is divided into hard charcoal and black wood charcoal.Specifically form as table 2.
Table 2
| The charcoal classification | C | H | O+N | Ash content |
| Hard charcoal | 90-96 | 0.1-2.4 | 2.00-6.57 | 1.04-3.66 |
| Black wood charcoal | 79-94 | 1.0-4.0 | 3.03-9.44 | 0.91-3.80 |
(3) condensable gases not
The not condensable gases that reaction obtains is a kind of inflammable gas, detects its composition with the gas phase chromatography, the results are shown in Table 3.
Table 3
| Project | N 2 | CO | CH 4 | CO 2 | O 2 | H 2 | H
2O and |
| Test | |||||||
| 1 | 4.01 | 26.06 | 5.79 | 8.80 | 0.94 | 2.75 | 8.65 |
| |
53.08 | 26.42 | 4.79 | 5.12 | 1.80 | 1.85 | 6.94 |
As shown in Table 3, not condensable gases mainly by CO, CH
4, CO
2, H
2Form with water vapour.N
2Be the carrier gas that feeds in the thermal cracking processes, O
2The air of bringing in the time of may being gas sampling.Condensable gases content mainly is not subjected to reaction temperatures affect, very easily burning, and its burning flare reaches more than the 1m, therefore can become the thermal source of thermal cracker by design.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (1)
1. the method for a preparing bio-oil by using rapid thermal cleavage technology, this method comprises carries out drying, pulverizing to material, material after will handling then is transported to by feed system and carries out heat scission reaction in the reactor, and the product that reaction obtains separated obtain described bio-oil, it is characterized in that this method is further comprising the steps of:
(a) at first under material and air state of contact, feed system with traditional screw propulsion method with mass transport in materials-stored box;
(b) with the material of materials-stored box by gas delivery to being provided with the adding in the hopper of the transmitter of determining material dosing;
(c) add transmitter in the hopper and determine that the accumulation degree of material reaches predetermined standard after, be arranged on the electronics open and close valve that adds on the hopper and close automatically and add the hopper top cover, make material be in anaerobic state; And
When (d) the electronics open and close valve that adds hopper is closed, the electronics open and close valve of feed bin is opened and the starting impulse feeding machine, material is sucked feed bin by pipeline, when sensors command feed bin electronics open and close valve was closed when the accumulation degree was up to standard, open the electronics open and close valve that adds hopper again, corresponding material is transported in the pyrolysis reactor by air pulse;
The water content of wherein said dried material is not more than 10%, and the particle diameter of the material after the pulverizing is 1-1.5mm, and the residence time of material in reactor is 0.5-3 second;
The top temperature of described heat scission reaction is 650 ℃, intensification is carried out stage by stage according to following program: the fs carries out under 120 ℃-150 ℃, subordinate phase is carried out under 150 ℃-280 ℃, and the phase III carries out under 280 ℃-450 ℃, and the quadravalence section is carried out under 450 ℃-650 ℃;
Wherein, product separates and comprises: the gaseous product that obtains in the pyrolysis reactor is transported to carries out condensation in the condenser system, collect the bio-oil that condensation obtains with biological oily holding tank then, and a non-condensable gas part that obtains is sent into circulating air compressor enter in the gas-holder, another part gas enters in the pyrolysis reactor as thermal source; The condenser that comprises two connections in the condenser system wherein, the temperature of first condenser are 50 ℃-70 ℃, and the temperature of second condenser is-2 ℃-2 ℃; Wherein said first condenser usually 1-2 in second with gas chilled to below 350 ℃, second condenser temperature under refrigeration is about 0 ℃, vertically is provided with between first condenser and second condenser.
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| CN104498065A (en) * | 2014-12-25 | 2015-04-08 | 刘荣 | High-efficiency biomass pyrolysis and purification technology |
| CN105316023A (en) * | 2015-12-03 | 2016-02-10 | 南京绿帝环保能源科技有限公司 | Oil sand cracking device |
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| CN115851296B (en) * | 2022-11-04 | 2024-06-21 | 中国农业科学院农业环境与可持续发展研究所 | Pyrolysis gas upgrading method based on Karman vortex |
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