CN101709224A - Biomass spiral pyrolysis device and pyrolysis process - Google Patents
Biomass spiral pyrolysis device and pyrolysis process Download PDFInfo
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Abstract
The invention relates to a biomass pyrolysis device and a process thereof. The device comprises a charging system, a spiral pyrolysis reactor and a product collection system, wherein a rotating shaft which is communicated with a variable-frequency motor and provided with a spiral propeller is arranged in center holes on two end covers of a cylinder body of the reactor; the side wall of the cylinder body is provided with a biomass feed pipe and a pyrolysis product outlet pipe; the outlet pipe is vertically extended into a coke collection tank; and the coke collection tank are communicated with a condenser, a bio-oil collection tank and a tail gas discharge pipe in turn through an air outlet pipe on the side wall. The process comprises the following technological processes: firstly, starting an external heating system to ensure that the temperature in a reactor is between 500 and 550 DEG C; secondly, putting biomass granular raw materials into the reactor through an inlet pipe, simultaneously starting the variable-frequency motor, and determining the rotating speed n of the variable-frequency motor according to the set residence time t, and the axial length L and the screw pitch l of the spiral propeller; and finally, starting the pyrolysis product collection system. The biomass pyrolysis device can accurately control the pyrolysis time and control the pyrolysis temperature in a partitioning mode so that the obtained bio-oil components are controllable and are easy to extract chemical products.
Description
Technical field
The present invention relates to the pyrolysis installation and the pyrolytic process of biomass.
Background technology
At present, countries in the world are developed country especially, for the Sustainable development that realizes national economy provides basic guarantee, all is being devoted to develop efficient, free of contamination biomass energy utilization technologies, to protect the fossil energy resource of this country.Biomass pyrolytic is meant that biomass are not having oxygenant (air, oxygen, water vapour etc.) to exist or only providing under the condition of limited oxygen, be heated to and exceed 500 ℃, biomass macromolecular substance (xylogen, Mierocrystalline cellulose and hemicellulose) is resolved into the thermochemistry transformation technology method of fuel material (solid-state charcoal, combustible gas, bio oil) by thermal chemical reaction than small molecules.The fuel energy transformation efficiency of biomass pyrolytic can reach 95.5%, to greatest extent biomass energy is converted into energy product, make the best use of everything, and pyrolysis also is burning and gasifies the requisite starting stage
From the angle of chemical reaction it is analyzed, complicated thermal chemical reaction has taken place in biomass in pyrolytic process, comprises reactions such as molecular scission, isomerization and small molecules polymerization.The main component of timber, forestry waste and agricultural waste material etc. is Mierocrystalline cellulose, hemicellulose and xylogen.Thermogravimetric analysis is the result show, Mierocrystalline cellulose begins pyrolysis in the time of 52 ℃, and along with the rising of temperature, pyrolytic reaction speeds up, and during to 350～370 ℃, is decomposed into low molecular product.According to the temperature variation of pyrolytic process and the situation of generation product etc., can be divided into drying stage, pre-pyrolysis stage, solid catabolic phase and calcination stage.Drying stage (temperature is 120～150 ℃), the moisture in the biomass evaporates, and the chemical constitution of material is almost constant.In the pre-pyrolysis stage (temperature is 150～275 ℃), the thermal response of material is apparent in view, and chemical constitution begins to change, and unstable constituents in the biomass such as hemicellulose resolve into materials such as carbonic acid gas, carbon monoxide and little acetic acid.Above-mentioned two stages are the thermo-negative reaction stage.Solid catabolic phase (temperature is 275～475 ℃), the pyrolytic main phase, physics, the chemical reaction of various complexity taken place in material, produces a large amount of degradation productions.Contain acetic acid, wood tar oil and methyl alcohol (separating out during cooling) in the product liquid that generates; CO2, CO, CH4, H2 etc. are arranged in the gaseous product, and combustiblecomponents content increases.This stage will be emitted a large amount of heat.Calcination stage (temperature is 450～500 ℃), biomass rely on the outside heat of supplying with to carry out the burning of charcoal, and the volatile matter in the charcoal is reduced, and fixed carbon content increases, and is exothermic phase.In fact, the boundary of above-mentioned four-stage is difficult to clearly divide, and the reaction process in each stage intersection is mutually carried out.
From heating rate and the angle of finishing the used time of reaction to biomass, biomass pyrolytic technology can be divided into two types basically: a kind of is pyrolysis at a slow speed, and a kind of is fast pyrogenation.In fast pyrogenation, when finish the reaction times very short (＜0.5s) time, be called the flash pyrolysis again.According to process conditions, biomass pyrolytic technology can be divided at a slow speed again, three kinds of quick and reactive pyrolysis.In slow pyrolysis process, can be divided into charing and conventional pyrolysis again.
Pyrolysis at a slow speed (claiming distillation process, traditional pyrolysis again) technology has history in several thousand, be a kind of be the carbonization process of purpose to generate charcoal, the Heating temperature of low-temperature pyrolysis is 500～580 ℃, and the medium temperature carbonization temperature is 660～750 ℃, and the temperature of high temperature carbonization is 900～1100 ℃.Timber is placed in the kiln, under the situation of secluding air, heats, can obtain accounting for the char yield of raw materials quality 30%～35%.
Fast pyrogenation is that the levigated biomass material is placed in the rapid pyrolysis apparatus, strict control heating rate (generally be roughly 10～200 ℃/s) and temperature of reaction (being controlled at about 500 ℃), biomass material is under the anoxybiotic situation, be rapidly heated to comparatively high temps, thereby cause macromolecular decomposition, produced micro-molecular gas and condensability volatile matter and a small amount of coke produced.The condensability volatile matter is cooled to flowable liquid fast, becomes bio oil or tar, and its ratio generally can reach 40%～60% of raw materials quality.
Compare with pyrolysis at a slow speed, the heat transfer reaction process of fast pyrogenation occurred in the extremely short time, and the intensive heat effect directly produces pyrolysis product, and quenching rapidly is chilled in 0.5s below 350 ℃ usually again, has increased liquid product (oil) to greatest extent.
Generally, influence the pyrolytic principal element and comprise chemistry and physics two broad aspect.Chemical factor comprises the primary first-order equation and the secondary reaction of a series of complexity; Physical factor mainly is the physical property of heat transfer, mass transfer and raw material in the reaction process etc.Concrete operational condition shows as: temperature, material characteristic, catalyzer, residence time, pressure and temperature rise rate.
In biomass pyrolysis process, temperature is a very significant effects factor, and it all has very big influence to pyrolysis product distribution, component, productive rate and pyrolysis gas calorific value.What of gas in the biomass pyrolytic final product, oil, each accounting example of charcoal have very big-difference with the height of temperature of reaction and the speed of rate of heating.In general, low temperature, long-term pyrolysis at a slow speed of being detained are mainly used in the output that increases charcoal to greatest extent, and its mass yield and energy productive rate reach 30% and 50% (massfraction) respectively.Temperature adopts medium speed of reaction during less than 600 ℃ conventional pyrolysis, and the productive rate of bio oil, non-condensable gas and charcoal is equal substantially; The flash pyrolysis temperature is mainly used to increase the output of bio oil in 500～650 ℃ of scopes, the bio oil productive rate can reach 80% (massfraction); Same flash pyrolysis if temperature is higher than 700 ℃, under residence time, is mainly used in the process gas product in very high speed of reaction and the gas phase of extremely lacking, and its productive rate can reach 80% (massfraction).When temperature rise rate was exceedingly fast, hemicellulose and Mierocrystalline cellulose generated charcoal hardly.
There is the branch of solid phase residence time and gas residence time residence time in the biomass pyrolytic reaction.The solid phase residence time is short more, and the shared ratio of pyrolytic solid product is just more little, and total product amount is big more, and pyrolysis is complete more.Under the condition of given temperature and temperature rise rate, the solid phase residence time is short more, and the solid product in the converted product of reaction is just few more, and the amount of gas-phase product is just big more.Gas phase time residence time does not generally influence a scission reaction process of biomass, and only has influence on the process of the second pyrolysis reaction of the bio oil generation in the liquid product.When a product in the biomass pyrolysis product enters in the gas phase of biological particles, further cracking reaction will take place in bio oil, in red-hot reactor, gas residence time is long more, it is just serious more that the second pyrolysis of bio oil takes place, and the second pyrolysis reaction increases, and emits H2, CH4, CO etc., cause liquid product to reduce rapidly, gaseous product increases.So, for obtaining maximum bio oil output, should shorten gas phase residence time, make the volatility product reactor that speeds away, reduce the time of secondarily cracking tar.
Conventional method for pyrolysis is that biomass material is placed in the existing pyrolysis installation in the prior art, for example fluidized bed pyrolysis.This pyrolysis normally is being lower than (0.1～1 ℃/s) under the condition, through the pyrolysis of several hrs, obtain accounting for 20%～25% biomass charcoal of raw materials quality and 30%～40% bio oil of 600 ℃ moderate temperature and medium speed of reaction.In fluidized-bed reactor, its solid particulate was fluidized state after biological particles was heated to suitable temp under the drive of nitrogen, biomass are finished pyrolytic process at 1-3 in the residence time of second, cleaved then various organism and coke enter cyclonic separator, coke separates the back and collects reuse, gas then enters condenser, promptly obtains the bio oil of complicated component after the condensation.Because the residence time of biological particles in fluidized-bed reactor can't accurately be controlled in the pyrolytic process, pyrolysis temperature also is difficult to control, therefore the pyrolysis product complicated component that obtains can't realize that pyrolysis product is the controlled of bio oil composition, is not easy refining and extracts chemical.That is to say that bio oil composition and concentration that existing pyrolytic technique obtains are at random.Therefore its bio oil that obtains can only be as low-grade fuel, and added value is lower, and this has limited the popularization of pyrolytic technique.
Summary of the invention
The objective of the invention is to, a kind of spiral pyrolysis installation and the pyrolytic process thereof that can accurately control biological particles pyrolysis time and pyrolysis temperature is provided, thereby effectively controls bio oil composition and concentration, make the biomass pyrolytic technology can further obtain promoting.
Biomass screw pyrolysis installation of the present invention, by charging system, pyrolysis reactor and pyrolysis product gathering system constitute, this pyrolysis reactor has outer heating system and heat-insulation system, it is characterized in that, described pyrolysis reactor is a spiral pyrolysis reactor, it comprises the garden shape cylindrical shell of two ends by the lid sealing, mesopore by two lids supports a rotation axis that can rotate with respect to garden shape cylindrical shell is installed, be provided with screw-blade on the rotation axis in cylinder chamber as spiral propeller, this screw-blade top and garden shape cylinder inboard wall face running fit, the external part of rotation axis outside the shape cylindrical shell of garden is connected with variable-frequency motor; On the shape cylinder lateral wall of garden, be respectively equipped with the outlet pipe of biomass feed-pipe and pyrolysis product, its feed-pipe is communicated with feeding warehouse, its outlet pipe vertically is passed in the coke holding tank of pyrolysis product gathering system, be provided with an outlet pipe on coke holding tank sidewall, this outlet pipe is communicated with condenser, bio oil holding tank, tail gas discharging pipe successively.Described outer heating system is the electric heating panel of power-adjustable, and is provided with thermocouple temperature measurement; The described pitch l that is installed in the spiral propeller on the rotation axis satisfies formula
Wherein, L is the axial length of spiral propeller, biomass the residence time helical reactors in of t for setting, be generally t=1-3 second, and n is the velocity of rotation of rotation axis, is generally 100-400 rev/min.
In the said apparatus, the outer heating system that described pyrolysis reactor has is an electric heating panel whole or isolating power-adjustable, and every electric heating panel is provided with thermometric thermopair.
In the said apparatus, described screw-blade as spiral propeller, garden shape cylinder inboard wall and rotation axis surface constitute by corrosion resistant material, to prevent to influence because of corrosion phenomenon the quality of bio oil.
Utilize spiral pyrolysis installation of the present invention that biomass are carried out the pyrolytic technological process, comprise the at first outer heating of startup system, make the reaction zone temperature in the spiral pyrolysis reactor be stabilized in 500-550 ℃; Again the biological particles raw material is delivered into spiral pyrolysis reactor by inlet pipe, it is characterized in that, start variable-frequency motor simultaneously, and according to the residence time t of biomass in spiral pyrolysis reactor that sets, and the axial length L of spiral pushing device and pitch l, use formula
Determine the rotation speed n of variable-frequency motor, velocity of rotation is in 100-400 rev/min of scope usually; Start the pyrolysis product gathering system then, can obtain liquid bio oil and other pyrolysis product.Described biological particles raw material is pulverized biological particles, and its particle diameter is the 20-200 order.
In actually operating, can suitably adjust the variable-frequency motor rotating speed then according to the attributional analysis of the bio oil that obtains, promptly adjust the residence time of biomass in helical reactors, to obtain suitable bio oil quality and yield.
Described " starting outer heating system; make the reaction zone temperature in the spiral pyrolysis reactor be stabilized in 500-550 ℃ ", can be helical reactors to be divided into different warm areas in the longitudinal direction by controlling different electric heating panels, be warming up to 550 ℃ gradually from 500 ℃ along biomass direction of motion, the productive rate of more favourable raising bio oil and oil product.
Spiral pyrolysis installation of the present invention carries out the pyrolytic technological process to biomass, compared with prior art, two major advantages is arranged:
(1) can control the residence time of biomass in the reactor device accurately:
The residence time of biomass in fluidized-bed reactor is general relevant with the useful volume of inlet amount and fluidized-bed reactor, it is a mean residence time, because the mixture kinestate complexity in the fluidized-bed, often there are short circuit, back-mixing and dead angle phenomenon, and because biological particles continuous weightlessness etc. in pyrolytic process, the residence time of biomass individuality is widely different.Therefore mean residence time can't accurately reflect the individual residence time.This spiral pyrolysis reactor is then fully different, as long as pitch reasonable in design, avoids material to skid and regurgitates phenomenon, then mean residence time just of the individual residence time of biomass.
Theoretically, biological particles is residence time difference in reactor, the asynchronism(-nization) that promptly reacts, and the composition of its pyrolyze product promptly can be had any different, and also is that bio oil composition and concentration can change.Spiral pyrolysis installation of the present invention, because the velocity of rotation of rotation axis can be regulated by variable-frequency motor, make the gait of march of biological particles, be that the residence time of biological particles in reactor can be precisely controlled, (can be accurate to 0.1 second), so the bio oil composition that pyrolysis obtains is more consistent with concentration ratio, and this further optimization for product has very big advantage.
(2) temperature of energy subregion control pyrolytic process:
According to the pyrolysis principle, biomass can improve the productive rate and the oil product of bio oil in different warm area pyrolysis.Because in biomass pyrolysis process, temperature is a very significant effects factor, and it all has very big influence to pyrolysis product distribution, component, productive rate and pyrolysis gas calorific value.What of gas in the biomass pyrolytic final product, oil, each accounting example of charcoal have very big-difference with the height of temperature of reaction and the speed of rate of heating.In general, low temperature, long-term pyrolysis at a slow speed of being detained are mainly used in the output that increases charcoal to greatest extent, and its mass yield and energy productive rate reach 30% and 50% (massfraction) respectively.If temperature is during less than 600 ℃ conventional pyrolysis and adopt medium speed of reaction, then the productive rate of bio oil, non-condensable gas and charcoal is equal substantially; If adopt the flash pyrolysis temperature in 500～650 ℃ of scopes, can increase the output of bio oil, the bio oil productive rate can be up to 80% (massfraction); Same flash pyrolysis if temperature is higher than 700 ℃, under residence time, can increase the gaseous product output in very high speed of reaction and the gas phase of extremely lacking, and its productive rate can reach 80% (massfraction).
Although fluidized bed pyrolysis reactor can adopt electrically heated, also can adopt the control of thermopair subregion, but because material is in fluidized state in the fluidized-bed, tend to occur air-teturning mixed phenomenon, the heat convection current is transmitted, make temperature in the reactor than uniform distribution, be difficult to by thermopair controlled temperature subregion.Do not have fluidisation and air-teturning mixed phenomenon in this spiral pyrolysis reactor, the heat transmission is fully by heat exchange pattern, so rate of heat transfer is little, is convenient to temperature control, and this helps the optimization of product.
The present invention directly generates bio oil with biomass pyrolytic by the spiral pyrolysis installation, not only is convenient to store transportation, and the bio oil controllable component, easily chemical is extracted in refining.
Below by embodiment and accompanying drawing the present invention is further described.
Description of drawings
Fig. 1 is the embodiment synoptic diagram of spiral pyrolysis installation of the present invention.
Embodiment
Referring to Fig. 1, one of the cylindrical shell 5 of garden barrel reactor is the flange plate-like, the two ends of playing the outer sleeve 6 of insulation effect also are the flange plate-like, cylindrical shell 5 and outer sleeve 6 set with each other, add that left and right sides two end cap 4,11 and threaded connector constitute an integral body, enough big gap is arranged between the outer wall of the inwall of outer sleeve 6 and cylindrical shell 5, and four electric heating panels 8 are arranged in this gap, and are enclosed on the outside wall surface of cylindrical shell 5.This electric heating panel is the electric heating panel of the power-adjustable of 4 * 1KW, respectively by four thermopairs 9 control, reach design temperature after, reduce heating power automatically, therefore the effective interior temperature of reaction (500-550 ℃) in certain scope of controlling reactor.Four thermopairs are independently controlled four hot-plates, can realize having in the helical reactors four different warm areas, to be implemented in the needs of differing temps on the shape cylindrical shell length direction of garden.One end of thermopair 9 contacts with the outside wall surface of cylindrical shell 5, and the other end passes outer sleeve and arrives space outerpace, connects instrument and observes with convenient.Biomass feed-pipe 7 is arranged on the top near left end, and its axis is vertical with cylindrical shell 5, and outlet pipe 12 is arranged on the below near right-hand member, and its axis is also vertical with cylindrical shell 5.In the central axis hole of left and right sides two end cap 4,11, rotation axis 3 is arranged, and high-temperature resistant seal ring 1 sealing is arranged by bearings.Variable-frequency motor 2 is connected with rotation axis 3 left ends, makes rotation axis 3 can follow electric machine main shaft and rotates together, and the rotating speed of this variable-frequency motor is adjustable in 100-400 rev/min of scope.The cylinder lumen that is inclusive at rotation axis partly is equipped with screw-blade 10, screw-blade top and cylinder inboard wall face running fit as spiral pushing device.It is 52 millimeters that present embodiment is selected cylinder internal diameter, and 50 millimeters of blade external diameters, rotation axis diameter are 30 millimeters; 240 millimeters of the length of screw propulsion part, the setting biomass residence time, in second, calculating pitch according to relevant formula was the 16-48 millimeter at 1-3, it is 30 millimeters that present embodiment is selected pitch, and has selected 15 ° of spiral pushing device helix angles commonly used for use.Outlet pipe 12 is passed in the coke holding tank 13 of below, connects into integral body by outlet pipe 14 and condenser 15, bio oil holding tank 16 and tail gas discharging pipe 17 then.
In the present embodiment, described screw-blade as spiral pushing device, garden barrel reactor and rotation axis are by the stainless material manufacturing.Described variable-frequency motor is buied by market, and model is CHF100-1R5G-4 (INVT ELECTRIC CO.LTD)
Utilize said apparatus to carry out practical application below and test relevant data.
Biomass material is a wood chip, is about the 40-80 order by the particle diameter after pulverizing.At first electric heating panel is heated to the temperature of setting: four thermopairs are set at 500 ℃ from left to right respectively, and 520 ℃, 530 ℃, 550 ℃, the actual temperature in the reactor has a little change.Then biomass material is joined the opening for feed of spiral pyrolysis reactor from feeder, start variable-frequency motor simultaneously, and open condenser and exhaust emissions system.Regulate rotation axis with 300 rev/mins rotational speed, i.e. 1.6 seconds residence time in reactor of biomass material.Biomass produce pyrolysis rapidly in reactor, its product is organic molecule gas and solid coke, spiral pushing device is released coke through outlet pipe in the coke holding tank, gas enters condenser through outlet pipe and from the air outlet of coke holding tank, obtain bio oil after the condensation and enter the bio oil holding tank, all the other tail gas are discharged from tail gas discharging pipe 5.
Concrete reaction conditions and related detection data are as follows:
The flow that enters of biomass material is 18 kilograms/hour, 8.6 kilograms/hour of the bio oil output that obtains.
The Preliminary detection analysis shows that bio oil water ratio＜30% that obtains, superior calorific value are 21MJ/kg.
Compare with the bio oil that fluidized bed pyrolysis of the prior art obtains, phenol content improves about 40% than fluidized bed pyrolysis in this spiral pyrolysis bio oil, and content reaches 22 kinds greater than 1% organism, and that uses common fluidized-bed has only the 10-15 kind.
Claims (7)
1. biomass screw pyrolysis installation, by charging system, pyrolysis reactor and pyrolysis product gathering system constitute, this pyrolysis reactor has outer heating system and heat-insulation system, it is characterized in that, described pyrolysis reactor is a spiral pyrolysis reactor, it comprises the garden shape cylindrical shell of two ends by the lid sealing, mesopore by two lids supports a rotation axis that can rotate with respect to garden shape cylindrical shell is installed, be provided with screw-blade on the rotation axis in cylinder chamber as spiral propeller, this screw-blade top and garden shape cylinder inboard wall face running fit, the external part of rotation axis outside the shape cylindrical shell of garden is connected with variable-frequency motor; On the shape cylinder lateral wall of garden, be respectively equipped with the outlet pipe of biomass feed-pipe and pyrolysis product, its feed-pipe is communicated with feeding warehouse, its outlet pipe vertically is passed in the coke holding tank of pyrolysis product gathering system, be provided with an outlet pipe on coke holding tank sidewall, this outlet pipe is communicated with condenser, bio oil holding tank, tail gas discharging pipe successively.
2. biomass screw pyrolysis installation as claimed in claim 1 is characterized in that, described outer heating system is an electric heating panel whole or isolating power-adjustable, and every electric heating panel is provided with thermometric thermopair.
3. biomass screw pyrolysis installation as claimed in claim 1 is characterized in that, the described pitch l that is installed in the spiral propeller on the rotation axis satisfies formula
Wherein, L is the axial length of spiral propeller, and biomass the residence time helical reactors in of t for setting, n is the velocity of rotation of rotation axis.
4. biomass screw pyrolysis installation as claimed in claim 1 is characterized in that described screw-blade as spiral propeller, garden shape cylinder inboard wall and rotation axis surface constitute by corrosion resistant material.
5. utilize spiral pyrolysis installation as claimed in claim 1 that biomass are carried out the pyrolytic technological process, comprise the at first outer heating of startup system, make the reaction zone temperature in the spiral pyrolysis reactor be stabilized in 500-550 ℃; Again the biological particles raw material is delivered into spiral pyrolysis reactor by inlet pipe, it is characterized in that, start variable-frequency motor simultaneously, and according to the residence time t of biomass in spiral pyrolysis reactor that sets, and the axial length L of spiral propeller and pitch l, use formula
Determine the rotation speed n of variable-frequency motor; Start the pyrolysis product gathering system then, can obtain liquid bio oil and other pyrolysis product.
6. technological process as claimed in claim 4 is characterized in that, described biological particles raw material is pulverized biological particles, and its particle diameter is the 20-200 order.
7. technological process as claimed in claim 4, it is characterized in that, described " starting outer heating system; make the reaction zone temperature in the spiral pyrolysis reactor be stabilized in 500-550 ℃ ", be helical reactors to be divided into different warm areas in the longitudinal direction, be warming up to 550 ℃ gradually from 500 ℃ along biomass direction of motion by controlling different electric heating panels.
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