CN2898028Y - Device for thermal cracking intermediate substance by cellulose - Google Patents

Device for thermal cracking intermediate substance by cellulose Download PDF

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Publication number
CN2898028Y
CN2898028Y CNU2006201003826U CN200620100382U CN2898028Y CN 2898028 Y CN2898028 Y CN 2898028Y CN U2006201003826 U CNU2006201003826 U CN U2006201003826U CN 200620100382 U CN200620100382 U CN 200620100382U CN 2898028 Y CN2898028 Y CN 2898028Y
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Prior art keywords
valve
quartz glass
glass tube
liquid nitrogen
mierocrystalline cellulose
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Expired - Lifetime
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CNU2006201003826U
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Inventor
王树荣
骆仲泱
岑可法
倪明江
方梦祥
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

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Abstract

The utility model discloses a device for the manufacture on the intermediate state material of cellulose thermal cracking. To place the xenon lamp on the focal spot of the ellipsoidal viewfinder, the light is converged to the plane mirror of 45 degree,downwards, a lens screen, a shutter and a quartz glass on the photocell with cellulose samples inside are connected with the device. The programmable controller is respectively connected with valve V1, V2,V3, V4 and V5,wherein, one end of V1 is connected with a nitrogen cylinder, one end of V2 is connected with the liquid nitrogen groove, the output terminals V1 and V2 are connected with those of V3 and V4 , the output terminal is connected with the end that connected with a terminal of the quartz glass tube, the other terminal is connected with the input end after being filtered, wherein the output end is connected with a gas chromatograph. The heat-up time for the sample of the utility model is controlled by the shutter. In order to accurately mensurate the heat-up time for the focal spot, where a photocell needs to be positioned, the switch between nitrogen and liquid nitrogen is controlled by the solenoid pilot actuated valve. The shuttle and the switch of solenoid pilot actuated valve are controlled by the PLC programmable controller.

Description

A kind of device for preparing Mierocrystalline cellulose thermo-cracking intermediate state material
Technical field
The utility model relates to a kind of device for preparing Mierocrystalline cellulose thermo-cracking intermediate state material.
Background technology
Energy and environment are two principal themes of current social development.The development of economic society is important motivity with the energy, and the overexploitation of fossil oil and use have brought huge pressure to environment protection.Biomass are as a kind of important renewable and clean energy resource resource, to help to alleviate the pressure of national economy fast development to its reasonable development and efficient utilization to energy demand, can overcome simultaneously the environmental pollution that traditional fossil oil utilizes in the process to be caused, thereby the emphasis paid close attention to of the persons that become the working energy beyond suspicion.
As the important component part of biomass thermal chemical conversion technology, the biomass through pyrolysis technology can be high-grade liquid fuel with Wood Adhesives from Biomass---bio oil and important chemical product are subjected to extensive concern to its research and application.Mierocrystalline cellulose has occupied almost half content as the main ingredient of biomass in biomass material, its thermo-cracking behavior embodies the thermo-cracking rule of biomass integral body to a great extent, and is therefore significant to the research of Mierocrystalline cellulose thermo-cracking mechanism.
The investigator has carried out a large amount of research to cellulosic thermo-cracking mechanism both at home and abroad, and " Broido-Shafizadeh " model is widely accepted.At a lower temperature, the process of a polymerization degree reduction fast of Mierocrystalline cellulose thermo-cracking experience, the intermediate state material of formation low polymerization degree; This material is extremely unstable under comparatively high temps, and lifetime is less than 1s, under the free radical effect further degraded can take place, and makes cellulose macromolecule enter into the pyrolytic main phase, generates tar, coke and micromolecular light gas then.Wherein coke is two parallel competing reactions with the generation of tar, and low temperature helps the generation of coke, and it is the condensability fugitive constituent of feature product that higher temperatures then is partial to generate with the Levoglucosan.
The proposition of intermediate state material in Mierocrystalline cellulose thermo-cracking mechanism model is the focus that research workers dispute on owing to do not provide compellent experiment support always.But Donald is by differential thermogravimetric analysis, about 180 ℃, find a little endotherm(ic)peak, and, show certain reaction has taken place under the low temperature really by the detection of infrared spectra to the cellulosic structure in the pyrolytic process, cellulosic structure is changed, thereby obtain a kind of intermediateness compound.And the strongest proof will give the credit to the early 21st century, and Boutin has observed directly a kind of material of molten state in his experiment, and just the existence for the intermediate state material provides true foundation.Detect and find that this material at room temperature is a kind of water miscible solid, but be different from flash pyrolysis oil (being in a liquid state under the room temperature), by the chromaticness on-line analysis, its component is simple relatively, and kind also obviously is less than the flash pyrolysis oil.This test-results has proved no matter the generation of this intermediate state material is to be presented as uncontrollable process in the flash cracker of high heating intensity, still these become the important step of controlling whole pyrolytic process in heating installation at a slow speed at thermobalance, cellulosic thermo-cracking all must have been passed through this important physicochemical change process, thereby make cellulose macromolecule enter into the pyrolytic main phase, generate tar, coke and micromolecular light gas then.
Result of study for many years shows, directly obtaining in thermobalance of this intermediate state material is impossible realize, and the flash thermal cracker be if can effectively control its further decomposition, just its certain existence of susceptible of proof, and its generation and evolution process furtherd investigate.
Summary of the invention
After a large amount of tests and theoretical investigation to Mierocrystalline cellulose thermo-cracking mechanism, the purpose of this utility model is to provide a kind of device for preparing Mierocrystalline cellulose thermo-cracking intermediate state material.
The technical solution adopted in the utility model is to comprise heating system and cooling, Controlling System, wherein:
1) heating system: the focus place that xenon lamp is placed on ellipsoidal mirror, light converges at 45 ° plane mirror after reflection, plane mirror is connected to diaphragm, shutter straight down successively, is placed on photronic quartz glass tube, the Mierocrystalline cellulose sample is placed in the monkey, and places on the quartz glass plate of airtight quartz glass tube;
2) cooling, Controlling System: the PLC programmable logic controller is connected with the first valve V1, the second valve V2, the 3rd valve V3, the 4th valve V4 and the 5th valve V5 circuit respectively, the termination nitrogengas cylinder of the first valve V1, the termination liquid nitrogen tank of the second valve V2, the output terminal of the first valve V1 and the second valve V2 is connected with the input terminus of the 3rd valve V3 and the 4th valve V4, one end of the output termination quartz glass tube of the 4th valve V4, the other end of quartz glass tube is through connecing the input terminus of the 5th valve V5, the output termination gas chromatograph of the 5th valve V5 behind the filter.
The beneficial effect that the utlity model has is:
1) the high pressure xenon short-act lamp is as a kind of comparatively ideal pointolite, by obtaining the high focus point of heat flow rate per unit area after the ellipsoidal mirror reflection, main body reactor adopting quartz glass pipe, to infrared almost transparent, a large amount of radiations heat energies sees through silica tube and is radiated on the material, satisfies and obtains the requirement of the needed flash intensification of intermediate state material pyrolytic;
2) because the intermediate state material is at high temperature extremely unstable, in the moment that heating finishes, utilize the principle of liquid nitrogen vaporization heat absorption that it is cooled to room temperature, obtain the intermediate state material of stable existence;
3) control by the rotary shutter of steel the heat-up time of sample, its high-temperature capability height, response are soon.For accurately measuring the heat-up time at focus place, at the focus place photocell is set, can accurately measure between the logical light time at focus place;
4) switching of nitrogen and liquid nitrogen is by the on-off control of magnetic valve in the reaction process, and the switch of each valve and shutter is by a PLC Controlled by Programmable Controller, and is easy to use, reliability is high, response is fast;
5) power input of adjusting xenon lamp can change the heat flow rate per unit area at focus place, adjusts the heat-up time that can change sample switching time of shutter, thus the degree that the control reaction is carried out;
6) volatile gases that adopts high pure nitrogen that reaction is emitted carries out reactor, and is through directly entering the gas chromatographic detection composition behind a small amount of tar of filter elimination, convenient and swift.
Description of drawings
Fig. 1 is the structural principle synoptic diagram of instantaneously heating and fast cooling set for cellulose;
Fig. 2 is that the A of Fig. 1 is to view;
Fig. 3 is the enlarged view of cooling system.
Among the figure: 1, xenon lamp, 2, ellipsoidal mirror, 3, fan, 4, plane mirror, 5, quartz glass tube, 6, the Mierocrystalline cellulose sample, 7, nitrogengas cylinder, 8, liquid nitrogen tank, 9, strainer, 10, PLC programmable logic controller, 11, gas chromatograph, 12, workplatform, 13, diaphragm, 14, shutter, 15, photocell, 16, soft rubber ball.
Embodiment
The utility model is described in further detail below in conjunction with drawings and Examples.
As Fig. 1, Fig. 2, shown in Figure 3, the utility model comprises heating system and cooling, Controlling System, wherein:
1) heating system: the focus place that xenon lamp 1 is placed on ellipsoidal mirror 2, light converges at 45 ° plane mirror 4 after reflection, plane mirror 4 is connected to diaphragm 13, shutter 14 straight down successively, is placed on the quartz glass tube 5 of photocell 15, the Mierocrystalline cellulose sample is placed in the monkey, and place on the quartz glass plate of airtight quartz glass tube 5, photocell 15 is placed on the workplatform 12;
2) cooling, Controlling System: PLC programmable logic controller 10 respectively with the first valve V1, the second valve V2, the 3rd valve V3, the 4th valve V4 is connected with the 5th valve V5 circuit, the termination nitrogengas cylinder 7 of the first valve V1, the termination liquid nitrogen tank 8 of the second valve V2, the output terminal of the first valve V1 and the second valve V2 is connected with the input terminus of the 3rd valve V3 and the 4th valve V4, one end of the output termination quartz glass tube 5 of the 4th valve V4, the other end of quartz glass tube 5 is through connecing the input terminus of the 5th valve V5, the output termination gas chromatograph 11 of the 5th valve V5 behind the filter 9.
The high pressure xenon short-act lamp 1 that it is 3kW that this testing apparatus adopts a power is as source of radiation, and its luminous point brightness is higher, is a kind of comparatively ideal pointolite.Its luminous point is placed on the first focus place of ellipsoidal mirror 2, and light converges at second focus of reflective mirror after reflection.A fan 3 is set, to the outside heat radiation, to guarantee xenon lamp 1 and ellipsoidal mirror 2 trouble-free services at the ellipsoidal mirror back.A light beam steering device is set in the light path, i.e. the plane mirror 4 of 45 ° of placements of one side, light beam converges at a border circular areas after reflection straight down.Mierocrystalline cellulose sample 6 is placed in the monkey, and places on the quartz glass plate of airtight quartz glass tube 5.Adjust whole optical path, make sample be positioned at the high focal spot of heat flow rate per unit area just.The shutter 14 that be 0.01s by a time of response heat-up time of sample is controlled.For accurately measuring the heat-up time at focus place, a photocell 15 is set at the focus place, determine that accurately its sensitivity is 0.01s between the logical light time at focus place.The Mierocrystalline cellulose sample 6 that takes a morsel is tiled in the crucible bottom surface, is placed on the focus place in the quartz glass tube 5, and soft rubber ball 16 makes reactive system be in closed state beyond the Great Wall, and connects total system.Open xenon lamp 1 and press the test arrangement power input, open PLC programmable logic controller 10 then, total system brings into operation by setup program.At first, the electrically heated rod energising in the liquid nitrogen tank 8, liquid nitrogen is heated to vaporize to make and produces certain pressure in the liquid nitrogen tank, opens valve V2, V3 liquid nitrogen is discharged smoothly; Valve-off V2, V3 open valve V1, V4, V5 then, make nitrogen be full of the entire reaction system, keep inert atmosphere; Valve-off V1, V4, V5, and moment open shutter 14, make the 6 flash pyrolysis of Mierocrystalline cellulose sample, when shutter 14 is closed by setting-up time, open valve V2, V4, V5, liquid nitrogen is sprayed onto sample surfaces rapidly it is cooled off; Valve-off V2 opens V1 subsequently, and nitrogen enters reactive system and the gaseous product purging is entered gas chromatograph 11 (as Agilent 6810 type gas chromatographs) and carries out analyzing and testing.Owing to may contain uncooled tar in the gaseous product, a strainer 9 is set, before entering gas chromatograph 11 in order to avoid damage instrument.
The most critical part:
1) the flash heating system of sample
The high pressure xenon short-act lamp that it is 3kW that this testing apparatus adopts a power is as source of radiation, and its luminous point brightness is higher, is a kind of comparatively ideal pointolite.Xenon lamp spectrum is the mixed light of wavelength 0.2~2.0 μ m, and the content of 0.8~1.0 μ m near-infrared radiation is higher, accounts for 78%, and visible light accounts for 12%, and ultraviolet ray accounts for 10%.Its luminous point is placed on the first focus place of ellipsoidal mirror, and light converges at second focus of reflective mirror after reflection.A light beam steering device is set in the light path, i.e. the plane mirror of 45 ° of placements of one side, light beam converges at a border circular areas after reflection straight down.Ellipsoidal mirror and plane mirror surface plating total reflection film aluminium film.The Mierocrystalline cellulose sample is placed in the monkey, and places airtight quartz glass tube, is convenient to picking and placeing of sample.Adjust whole optical path, make sample be positioned at the high focal spot of heat flow rate per unit area just.The heat flow rate per unit area at focus place can be regulated by the power input that changes xenon lamp.
2) accelerate cooling system of sample
Because the intermediate state material is at high temperature extremely unstable,, need it is cooled to room temperature in the moment that heating finishes.This testing apparatus utilizes the principle of liquid nitrogen vaporization heat absorption that it is cooled off.The vaporization of being heated of the electrically heated rod that in the liquid nitrogen storage tank three power to be set be 1kW, liquid nitrogen makes and produces certain pressure in the liquid nitrogen tank, and when valve opening, liquid nitrogen just can spray and be used to cool off sample.
3) Controlling System
Control by shutter the heat-up time of sample.The shutter that this device adopts is the rotary shutter of steel, and its time of response is 0.01s.For accurately measuring the heat-up time at focus place, at the focus place photocell is set, its sensitivity is 0.01s.The switching of nitrogen and liquid nitrogen is controlled by the magnetic valve in the light path.And the switch of shutter and magnetic valve is by a PLC Controlled by Programmable Controller.
At first take by weighing a certain amount of cellulose substances in the process of the test and be tiled in the crucible bottom surface, be placed on the focus place in the quartz glass tube, stopper makes reactive system be in closed state beyond the Great Wall, and connects piping system.Open xenon lamp and press the test arrangement power input, open the PLC programmable logic controller then, total system brings into operation by setup program.At first, the electrically heated rod energising in the liquid nitrogen tank, liquid nitrogen is heated to vaporize to make and produces certain pressure in the liquid nitrogen tank, opens valve V2, V3 liquid nitrogen is discharged smoothly; Valve-off V2, V3 open valve V1, V4, V5 then, make nitrogen be full of the entire reaction system, keep inert atmosphere; Valve-off V1, V4, V5, and moment open shutter, make the pyrolysis of Mierocrystalline cellulose sample flash, when shutter is closed by setting-up time, open valve V2, V4, V5, liquid nitrogen is sprayed onto sample surfaces rapidly it is cooled off; Valve-off V2 opens V1 subsequently, and nitrogen enters reactive system and the gaseous product purging is entered gas-chromatography and carries out analyzing and testing.Owing to may contain uncooled tar in the gaseous product, a strainer is set, before entering gas-chromatography in order to avoid damage instrument.After the off-test, cellulosic crucible will be housed take out, sample wherein is water-soluble.Utilize the intermediate state material water-soluble and the water-fast character of Mierocrystalline cellulose is separated with unreacted Mierocrystalline cellulose this intermediate state material by filtering solution with coke produced.The aqueous solution is dried under 45 ℃ of temperature, can obtain the solid intermediate state material of stable existence.

Claims (2)

1, a kind of device for preparing Mierocrystalline cellulose thermo-cracking intermediate state material is characterized in that comprising heating system and cooling, Controlling System, wherein:
1) heating system: the focus place that xenon lamp (1) is placed on ellipsoidal mirror (2), light converges at 45 ° plane mirror (4) after reflection, plane mirror (4) is connected to diaphragm (13), shutter (14) straight down successively, is placed on the quartz glass tube (5) on the photocell (15), the Mierocrystalline cellulose sample is placed in the monkey, and places on the quartz glass plate of airtight quartz glass tube (5);
2) cooling, Controlling System: PLC programmable logic controller (10) respectively with the first valve V1, the second valve V2, the 3rd valve V3, the 4th valve V4 is connected with the 5th valve V5 circuit, the termination nitrogengas cylinder (7) of the first valve V1, the termination liquid nitrogen tank (8) of the second valve V2, the output terminal of the first valve V1 and the second valve V2 is connected with the input terminus of the 3rd valve V3 and the 4th valve V4, one end of the output termination quartz glass tube (5) of the 4th valve V4, connect the input terminus of the 5th valve V5 behind the other end process filter (9) of quartz glass tube (5), the output termination gas chromatograph (11) of the 5th valve V5.
2, a kind of device for preparing Mierocrystalline cellulose thermo-cracking intermediate state material according to claim 1, it is characterized in that: described xenon lamp (1) is the high pressure xenon short-act lamp of 3kW, spectrum is the mixed light of wavelength 0.2~2.0 μ m.
CNU2006201003826U 2006-01-16 2006-01-16 Device for thermal cracking intermediate substance by cellulose Expired - Lifetime CN2898028Y (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100365202C (en) * 2006-01-16 2008-01-30 浙江大学 Instantaneously heating and fast cooling set for cellulose
CN104327301A (en) * 2014-10-15 2015-02-04 华东理工大学 Device for recycling carbon fiber by sunshine secondary reflection and method
CN106221848A (en) * 2016-09-29 2016-12-14 太原理工大学 The fixed bed reactors bakeed for biomass

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100365202C (en) * 2006-01-16 2008-01-30 浙江大学 Instantaneously heating and fast cooling set for cellulose
CN104327301A (en) * 2014-10-15 2015-02-04 华东理工大学 Device for recycling carbon fiber by sunshine secondary reflection and method
CN104327301B (en) * 2014-10-15 2017-01-18 华东理工大学 Device for recycling carbon fiber by sunshine secondary reflection and method
CN106221848A (en) * 2016-09-29 2016-12-14 太原理工大学 The fixed bed reactors bakeed for biomass
CN106221848B (en) * 2016-09-29 2019-02-19 太原理工大学 The fixed bed reactors baked for biomass

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AV01 Patent right actively abandoned

Effective date of abandoning: 20080130

C25 Abandonment of patent right or utility model to avoid double patenting