CN105806735A - Macroalgae pyrolysis characteristic and pyrolysis kinetic research method - Google Patents
Macroalgae pyrolysis characteristic and pyrolysis kinetic research method Download PDFInfo
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- CN105806735A CN105806735A CN201410834733.5A CN201410834733A CN105806735A CN 105806735 A CN105806735 A CN 105806735A CN 201410834733 A CN201410834733 A CN 201410834733A CN 105806735 A CN105806735 A CN 105806735A
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Abstract
The invention discloses a macroalgae pyrolysis characteristic and pyrolysis kinetic research method and belongs to the field of biochemical engineering. The research method has conditions of a macroalgae pyrolysis temperature range, a weight loss rate and heat effect characteristic parameters. Preferably, the macroalgae pyrolysis characteristic and pyrolysis kinetic research method can acquire the optimal pyrolysis mechanism function according to thermal analysis data. The research method can provide reference for biomass pyrolysis theoretical model building and provide theoretical and experimental basis for design, selection and optimization of various pyrolysis technologies and equipment of marine biomass.
Description
Technical field
The present invention relates to a kind of pyrolyzing large-scale seaweed characteristic and pyrolysis kinetics research, belong to biological chemical field.
Background technology
Biomass energy is a kind of important Renewable resource, and pyrolysis is the most promising a kind of biomass economy mode in future.By the pyrolysis kinetics research to biomass, it is possible to obtain kinetics of Thermolysis parameter, significant for judging pyrolytic reaction mechanism and influence factor and optimization reaction condition.Ocean area accounts for the 71% of earth surface, containing abundant living resources, wherein Sargassum is extended familys of living marine resources, there are 250 genus, more than 1500 plant all right artificial culture of Sargassum, China is algal cultivation the first big country in the world, annual production reaches more than 1,220,000 ton dry weights, account for sea-farming total output 11.5% Sargassum in containing abundant organic and inorganic substances, except abundant food and medicine can be provided, Sargassum can also provide biomass energy for people, utilize the residue pyrolysis bio oil in cheap fast-growing Sargassum or Sargassum can realize the comprehensive utilization of Sargassum, the economic worth of Sargassum can be improved, can effectively protect the marine environment again.Therefore, as the biology energy, there is important strategic importance using Sargassum.
At present, the biomass such as wooden class, house refuse have been studied by a lot of experts and scholars.But China is less for the biomass research of tangleweed, tangleweed biomass energy can directly or mix and make moulded coal, for stove, stove burning.Clean energy resource can also be become by state-of-the-art technologys such as materialization, biochemical conversions to use.Adopt non-isothermal Thermogravimetric analysis that tangleweed is carried out general reaction kinetics to study.By studying its pyrolysis characteristics, inquiring into the factor such as heating rate, the particle diameter affecting laws to large-scale chlorella Enteromorpha clathrata (Roth) Greville pyrolysis, and on experiment basis, the pyrolysis kinetics equation of preliminary study Sargassum and parameter, this still belongs to precedent at home.
Pyrolysis is a kind of important process of abandoned biomass recycling, be at present bio oil by pyrolysis by Biomass being the Main way utilizing biomass, especially the fast pyrogenation of biomass and catalysis pyrolysis enjoy the concern of researcher to be also most possibly for the technology in biomass pyrolytic preparing bio-oil industrialized development.The research of the catalysis pyrolysis of biomass and fast pyrogenation and low cost, efficient reaction unit becomes the research topic that comparison is popular, experiments show that, add catalyst and be possible not only to reduce the primary temperature of volatile matter, but also the composition of thermal decomposition product can be affected, in product, gas content increases, content liquid reduces, and is suitable for the pyrolytic process of product for the purpose of pyrolysis gas.The heat chemistry material of terrestrial life matter resource has been carried out widely studied by current scientist, and has been set up the pyrolysis kinetic model being correlated with.But, up to the present still very limited and focus mostly in the research for microalgae for marine organisms Quality Research, research finds the commercial application having a lot of technical barriers to constrain microalgae preparing bio-oil, as: how large-scale culturing micro-algae is to obtain higher Biomass, how to increase the oil content of microalgae and reduce the cost of application and the microalgae reactor etc. of excellent in design, so at present more researcher has turned one's attention to the marine biomass of more potentiality, its Biomass be very huge this just significantly solve raw material carry out source problem.
The present invention adopts thermogravimetry that pyrolytic process and the dynamic law thereof of two kinds of tangleweed biomass one Entermorpha and chlorella have been studied, and the utilization for seaweed bio mass-energy is laid a good foundation.Analyze sample impact on seaweed biomass pyrolysis characteristics under different 10,20,30 DEG C/min of heating rate, establish pyrolysis kinetic model.
Summary of the invention
The present invention is based on different in composition structure and chemical composition of marine biomass and terrestrial life matter, with Entermorpha and Macrocystis pyrifera (L.) Ag. waste residue for main study subject and with straw and Jerusalem artichoke for comparison, by to these four biomass pyrolytic dynamics research, obtain kinetics of Thermolysis parameter, for judging pyrolytic reaction mechanism and influence factor and optimizing significant.
In order to realize above goal of the invention, the technical scheme that the present invention takes is as follows:. a kind of pyrolyzing large-scale seaweed characteristic and pyrolysis kinetics research, including following condition:
Understand the characterisitic parameters such as the pyrolysis temperature range of Sargassum, weight loss rate and heat effect.
As preferably: best pyrolysis mechanism function can also be judged according to heat analysis data.
As preferably: the kinetic parameters such as pyrolytic reaction activation energy can also be asked for.
As preferably: utilize reaction designing to provide certain basic data for the thermochemical study of Sargassum.
As preferably: the thermochemical study of Sargassum utilizes the basic data that optimization of operating condition offer is certain.
Beneficial effects of the present invention is as follows: the foundation being possible not only to form biomass pyrolysis theoretical model provides reference, it is also possible to provide fundamental basis and experimental basis for the various pyrolytic process of marine biomass from now on and the design of equipment, selection and optimization.
Accompanying drawing explanation
Fig. 1 is that Entermorpha is at the TG-DTG-DSC curve that heating rate is during 10 DEG C/min；
Fig. 2 is that straw is at the TG-DTG-DSC curve that heating rate is during 10 DEG C/min；
Fig. 3 is that Jerusalem artichoke is at the TG-DTG-DSC curve that heating rate is during 10 DEG C/min；
Fig. 4 is that Macrocystis pyrifera (L.) Ag. is at the TG-DTG-DSC curve that heating rate is during 10 DEG C/min.
Detailed description of the invention
For making the purpose of the present invention, technical scheme and advantage clearly understand, develop simultaneously embodiment referring to accompanying drawing, the present invention is described in further details.
Major experimental material and reagent
Raw material
(1) Entermorpha (in August, 2008 picks up from Huiquan Bay of Qingdao, and Entermorpha belongs to Chlorophyta, Ulvales, Ulvaceae, Enteromorpha)；
(2) Macrocystis pyrifera (L.) Ag. (in March, 2011 picks up from Jiangnan, Qingdao bright moon Sargassum group company, Macrocystis pyrifera (L.) Ag. Phaeophyta, Macrocystis pyrifera (L.) Ag. section)；
(3) straw (in JIUYUE, 2008 picks up from farmland near University Of Science and Technology Of Shandong)；
(4) Jerusalem artichoke (in April, 2009 picks up from Liaocheng of Shandong Province).
Key instrument and equipment
(1) FC204 electronic analytical balance (Shanghai precision balance company limited)
(2) 101-1AB electric heating constant-temperature blowing drying box (Longkou City's electric furnace factory)
(3) DL-5-B centrifuge (Shanghai City An Ting scientific instrument factory)
(4) water bath with thermostatic control (Jintan Dadi Automation Equipment Factory)
(5) 50ml acid buret
(6) 50ml base buret etc.
(7) electric furnace
(8) elemental analyser
(9) SX2 chamber type electric resistance furnace (Longkou City's electric furnace maker)
(10) KSY-D-16 resistance temperature controller (Longkou City's electric furnace maker)
(11) exsiccator (built-in variable color silica gel)
(12) glass weighing botle (diameter 40mm, high 25mm, and with tight ground lid)
(13) common round bottom crucible (20ml)
(14) round bottom crucible with cover (Determination of Volatile Matter is special, and cover rim has volatile matter gas outlet)
(15) Crucible tongs, tripod, tripod folder, stopwatch.
Main agents
Glacial acetic acid (AR, Tianjin chemical reagent three factory)
Nitric acid (AR, Tianjin Kermel Chemical Reagent Co., Ltd.)
Sulphuric acid (AR, Tianjin Kermel Chemical Reagent Co., Ltd.)
Sodium dichromate (AR, Tianjin Kermel Chemical Reagent Co., Ltd.)
Potassium iodide (AR, Tianjin Jin Bei Fine Chemical Co., Ltd)
Soluble starch (AR, Shantou Xilong Chemical Factory Co., Ltd)
Sodium thiosulfate (CP, Jinan City's red flag the 3rd chemical plant)
Hydrochloric acid (AR, Tianjin Kermel Chemical Reagent Co., Ltd.)
Natrium carbonicum calcinatum (AR, Rui Jin, Tianjin spy Chemical Company)
Experimental technique
(1) reagent: the mixed liquor of nitric acid and acetic acid, the sulphuric acid of mass fraction 10%, 0.1M sodium dichromate solution, mass fraction 20%KI, mass fraction 0.5% soluble starch, 0.2M hypo solution
null(2) measure: after being pulverized by Caulis et Folium Oryzae, cross 100 mesh sieves，Weigh 0.05～0.10g (numerical value is designated as n) biomass material to be placed in test tube，Above-mentioned test tube adds the mixed liquor of 5ml acetic acid and nitric acid，Tampon beyond the Great Wall，Put heating 25min in boiling water，And be stirred continuously，It is centrifuged after cooling，Abandoning supernatant，Precipitation uses distilled water flushing 3 times，The sulphuric acid of 10ml mass fraction 10% and the sodium dichromate solution of 10ml0.1mol/l is added in precipitation，Shake up，Enter 10min in boiling water，Pour in triangular flask after taking-up，And with appropriate distilled water flushing test tube 3 times，Pour in the lump in triangular flask，5ml mass fraction 20%KI solution and 1ml mass fraction 0.5% starch solution is added after solution cools down，With 0.2mol/l sodium thiosulfate solution titrated (iodimetric titration)，And by above-mentioned steps do other two parallel，Additionally，Independent titration adds the sodium dichromate solution of 10ml mass fraction 10% sulphuric acid and 10ml0.1mol/l，By 0.2mol/l sodium thiosulfate solution titrated as blank.
(3) result represents: cellulosic content is calculated as follows:
X=K (a-b)/24n
In formula: " 24 " are 1molC6H10O5Be equivalent to the equivalents of sodium thiosulfate；K is the concentration of sodium thiosulfate, mol/L；A is consumed sodium thiosulfate volume, ml by blank titration；B is the volume of the consumed sodium thiosulfate of solution, ml；N is biomass material quality, g.
Result and discussion
Biomass material Analysis of Pyrolytic Properties result can obtain three kinds of curves under certain heating rate: (1) thermogravimetric curve (TG curve).Abscissa is temperature, and vertical coordinate is percent weight loss.(2) differential thermogravimetric curve (DTG curve).Abscissa is temperature, and vertical coordinate is the rate of change of quality, and TG curve is asked first derivative to obtain by it, the rate of change of reaction mass and the relation of temperature.It can clearly reflect the temperature etc. of initial reaction temperature, maximum reaction rate and correspondence thereof.(3) differential scanning curve (DSC curve).Abscissa is temperature, and vertical coordinate is the difference power of sample and reference substance, upwards represents heat release, represents downwards heat absorption.
From four kinds of biomass heating rate be TG-DTG curve during 10 DEG C/min it can be seen that along with the rising of temperature, the pyrolysis of biomass has four-stage:
(1) first stage is moisture precipitation phase, and its temperature range is respectively as follows: Entermorpha 320～440K, Macrocystis pyrifera (L.) Ag. 320～420K, straw 320～390K, Jerusalem artichoke 320～386K.Along with in the rising biomass of temperature, moisture starts to precipitate out, there is fluctuation in difference quotient curve；
(2) second stage is slow catabolic phase, and its temperature range is respectively as follows: Entermorpha 440～520K, Macrocystis pyrifera (L.) Ag. 420～520K, straw 390～473K, Jerusalem artichoke 386～524K.In this region, there occurs the weightlessness of trace, it may be possible to there occurs depolymerization, prepare for fast pyrogenation, at this moment discharge micromolecular compound, such as CO, CO2 and H2 etc..
(3) three phases are the fast pyrogenation stages, are the Main Stage of pyrolysis, and the major part of sample is weightless to be occurred in this region, and weight-loss ratio accounts for more than the 80% of whole weightlessness.DTG curve also there occurs obvious peak value in this region.The temperature range in this region is: Entermorpha 520～835K, Macrocystis pyrifera (L.) Ag. 520～815K, straw 473～775K, Jerusalem artichoke 386～760K.
(4) four-stages are slowly decomposition and the volatilization process of residue and inorganic ash content.
The DSC curve of four kinds of biomass have recorded thermal power variation with temperature in experimentation, and DSC is on the occasion of being expressed as pyrolytic reaction heat absorption, otherwise then for heat release.First peak of DSC curve and the temperature corresponding to first peak of DTG curve all very close to, illustrates there is corresponding relation, namely there is corresponding relation in the moisture precipitation process of biomass and endothermic process.And biomass had an obvious endothermic peak before there is primary response, it was shown that the sufficient pyrolysis of going deep into that heat absorption is biomass provides necessary preparation.
Four kinds of biomass thermogravimetric curves are substantially all divided into four pyrolysis Characteristics sections, but the thermogravimetric curve of Entermorpha and Macrocystis pyrifera (L.) Ag. shows more abundant details.Entermorpha and Macrocystis pyrifera (L.) Ag. have three fairly obvious division peaks, it was shown that Entermorpha has the construction unit that multiple degree of heat stability is different with Macrocystis pyrifera (L.) Ag..The heat stability of Entermorpha and Macrocystis pyrifera (L.) Ag. is significantly lower than terrestrial organism matter.
Brief summary
(1) analysis to Sargassum pyrolysis characteristics curve is passed through it can be seen that Sargassum pyrolysis can be divided into four-stage: the first stage occurred before 150 DEG C is mainly the dehydration process of sample；150 DEG C-200 DEG C slow processes that depolymerization and " glass transition " phenomenon occur；It is the major pyrolytic stage in the phase III of 200 DEG C of one 400 DEG C of temperature ranges, precipitates out substantial amounts of volatile matter in this stage, form violent weightless process；Happens is that the fourth stage of pyrolysis after 400 DEG C, be that residual substance continues pyrolysis phase slowly, mainly generate ash in this stage.
(2) the more land lignocellulosic biomass of seaweeds biomass volatile matter relatively early precipitates out, and is mainly soluble polysaccharide and protein；Heating rate is to affect the principal element that biomass pyrolytic is weightless, and along with heating rate increases, the maximum pyrolysis rate value of Sargassum increases, and TG and DTG curve all moves to high temperature side, and maximum weight loss rate reduces corresponding peak temperature island.Rear shifting, namely shows～fixed retardance, but heating rate is more high, and the response time is more short, and pyrolysis characteristics index increases.
(3) particle diameter differs for the impact of seaweed sample, determining mainly due to sample morphology structure, differing of surface area hole determines the speed of pyrolysis, Enteromorpha clathrata (Roth) Greville and chlorella when below 0.45mm, change of size is inconspicuous on pyrolytic process impact, slightly affects.
(4) in biomass material, ash and volatile matter are very big to pyrolysis behavioral implications.Ash is more big, and the pyrolysis temperature temperature corresponding with reaching maximum pyrolysis rate is more low；Volatile matter is more big, and maximum pyrolysis rate is more high.
Those of ordinary skill in the art is it will be appreciated that embodiment described here is to aid in the implementation of the reader understanding present invention, it should be understood that protection scope of the present invention is not limited to such special statement and embodiment.Those of ordinary skill in the art can make various other various concrete deformation and combination without departing from essence of the present invention according to these technology disclosed by the invention enlightenment, and these deformation and combination remain in protection scope of the present invention.
Claims (5)
1. pyrolyzing large-scale seaweed characteristic and a pyrolysis kinetics research, is characterized in that: understand the characterisitic parameters such as the pyrolysis temperature range of Sargassum, weight loss rate and heat effect.
2. a kind of pyrolyzing large-scale seaweed characteristic according to claim 1 and pyrolysis kinetics research, is characterized in that: can also judge best pyrolysis mechanism function according to heat analysis data.
3. a kind of pyrolyzing large-scale seaweed characteristic according to claim 1 and pyrolysis kinetics research, is characterized in that: can also ask for the kinetic parameters such as pyrolytic reaction activation energy.
4. a kind of pyrolyzing large-scale seaweed characteristic according to claim 1 and pyrolysis kinetics research, is characterized in that: the basic data utilizing reaction designing offer certain for the thermochemical study of Sargassum.
5. a kind of pyrolyzing large-scale seaweed characteristic according to claim 1 and pyrolysis kinetics research, is characterized in that: the thermochemical study of Sargassum utilizes the basic data that optimization of operating condition offer is certain.
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| CN106908476A (en) * | 2017-01-20 | 2017-06-30 | 内蒙古科技大学 | Gangue prepares the rapid assay methods of concrete admixture optimum calcinating temperature |
| CN108985006A (en) * | 2018-08-03 | 2018-12-11 | 中国科学技术大学 | Pyrolysis Kinetics Parameter and mechanism function acquisition methods under multiple heating mode |
| CN109580421A (en) * | 2019-01-03 | 2019-04-05 | 东北大学 | The volatile matter release characteristics index calculation method of difficult pyrolytic material |
| FR3097554A1 (en) * | 2019-06-24 | 2020-12-25 | Europeenne De Biomasse | Process for the production of a biofuel by steam cracking |
| FR3097555A1 (en) * | 2019-06-24 | 2020-12-25 | Europeenne De Biomasse | Process for the production of a biofuel by steam cracking |
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- 2014-12-29 CN CN201410834733.5A patent/CN105806735A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106908476A (en) * | 2017-01-20 | 2017-06-30 | 内蒙古科技大学 | Gangue prepares the rapid assay methods of concrete admixture optimum calcinating temperature |
| CN108985006A (en) * | 2018-08-03 | 2018-12-11 | 中国科学技术大学 | Pyrolysis Kinetics Parameter and mechanism function acquisition methods under multiple heating mode |
| CN109580421A (en) * | 2019-01-03 | 2019-04-05 | 东北大学 | The volatile matter release characteristics index calculation method of difficult pyrolytic material |
| FR3097554A1 (en) * | 2019-06-24 | 2020-12-25 | Europeenne De Biomasse | Process for the production of a biofuel by steam cracking |
| FR3097555A1 (en) * | 2019-06-24 | 2020-12-25 | Europeenne De Biomasse | Process for the production of a biofuel by steam cracking |
| WO2020260801A1 (en) | 2019-06-24 | 2020-12-30 | Europeenne De Biomasse | Method for producing a biofuel by steam cracking |
| WO2020260798A1 (en) | 2019-06-24 | 2020-12-30 | Europeenne De Biomasse | Method for producing a biofuel by steam cracking |
| CN114585713A (en) * | 2019-06-24 | 2022-06-03 | 欧洲生物质能公司 | Method for producing biofuel by steam cracking |
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