CN101121895A - Biological oil and method for preparing the same by biomass magnetic stabilization fluidized bed reactor middle-temperature fast hot crack - Google Patents
Biological oil and method for preparing the same by biomass magnetic stabilization fluidized bed reactor middle-temperature fast hot crack Download PDFInfo
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- CN101121895A CN101121895A CNA2007101473252A CN200710147325A CN101121895A CN 101121895 A CN101121895 A CN 101121895A CN A2007101473252 A CNA2007101473252 A CN A2007101473252A CN 200710147325 A CN200710147325 A CN 200710147325A CN 101121895 A CN101121895 A CN 101121895A
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Abstract
The invention relates to a biological oil and a method to produce biologic oil by rapid cracking under mid-temperature through a biomass magnetic-stable fluid-bed reactor. The biological oil consists of (calculated by weight percent) C (more than 71.1 percent), H (more than 7.3 percent), O (16.6 percent) and N (0.1 percent); oil viscosity (more than 106mPa.s), pH value (bigger than 2.5), and water content (less than 20 percent). In terms of production method, biomass materials (straws, leaves, saw dust, organic wastes) are cracked rapidly in a magnetic-stable fluid-bed reactor under an intermediate temperature; gas-solid separation is conducted through a cyclone separator; the gas is condensed, and biological oil is achieved after simple hydrogenation of the condensed liquid and distillation, and the production rate is as high as 75 percent. The biological oil consists of rich chemical elements (phenol, aldehyde substance), and the economic value is relatively high. The technology adopts biomass as raw materials and such materials can be achieved easily; the price is low, the technical process is simple, the application and market prospect are promising; and the invention can settle environmental problems efficiently and increase the income of farmers. Therefore, the invention meets the requirements of sustainable development.
Description
Technical field:
The present invention relates to a kind of bio oil and with the method for warm fast pyrolysis system bio oil in the biomass magnetic stabilization fluid bed bioreactor, belong in the biomass engineering the middle temperature Rapid Thermal in the biomass thermal chemical conversion and decompose the field.
Background technology:
The biomass fast pyrolysis liquefaction technology is one of cutting edge technology in world today's renewable energy source development field.Product can obtain the energy (being the highest means of present utilization ratio) of primordial matter 85%～90% based on bio oil.Bio oil also can be passed through further separation, extraction, synthetic high added value industrial chemicals except that as the fuel.
Reactor and modified version thereof are bored in the rotation that has that is used for the pyrolysis reactor input scale production of production bio oil at present, fluidized-bed reactor etc., but mostly have certain shortcoming.Rotation awl reactor as Dutch Twente university student's material technology group does not need carrier gas, and the device volume is little, bio oil productive rate height, but the equipment operation is complicated with maintenance, the energy consumption height.The fluidized-bed reactor of Canada Waterloo university, apparatus and process is simple, and response intensity is big, heat and mass speed height, the temperature field is even, but the bed material easily runs off, and easily lumps with material.
Summary of the invention:
The purpose of this invention is to provide a kind of bio oil and utilizing a kind of reactor is the method for warm fast pyrolysis system bio oil in the biomass magnetic stabilization fluid bed bioreactor, this invention is that to utilize a kind of new reactor be magnetic stabilization fluid bed bioreactor system bio oil, overcome the shortcoming of conventional flow fluidized bed reactor, realize the technology simple and stable, processing power is strong, oil productive rate height, characteristic of low energy consumption.Magnetic stabilization fluid bed is to be the bed material with the magnetic-particle, the stable bed that forms under the uniform magnetic field of axial time-independent space.The magnetic stabilization fluid bed many advantages that have fixed bed and fluidized-bed concurrently.It can use the small-particle solid and be unlikely to cause too high pressure to fall as fluidized-bed, alternate back-mixing has been controlled in the effect of externally-applied magnetic field effectively, and the flowable of fine particle makes the loading and unloading solid very convenient; Can avoid in the fluidized bed process solid particulate loss phenomenon that often occurs, also can avoid the hot localised points that may occur in the fixed bed, simultaneously can stable operation in relative broad range, can also brokenly lump and improve interphase mass transfer.
The objective of the invention is to realize in the following manner:
Contain C＞71.1%, H＞7.3%, O＞16.6%, N＜0.1% in the bio oil of the present invention by mass percentage, oil viscosity＞10
6MPa.s, density＞1.10, pH value＞2.5, water ratio＜20%.
Adopt international advanced middle temperature fast pyrolysis technology, with magnetic stabilization fluid bed (bed material: thin iron sand powder, particle diameter＜0.2mm.Externally-applied magnetic field: coil is set, realizes Digital Control, uniform magnetic field is provided.) be reactor system bio oil.Biomass fast by the magnetic stablizing bed material of high temperature, have reduced residence time of material under the rheomorphism of Poor oxygen gas, suppressed the product secondary and decomposed generation gas, and the bio oil productive rate has improved nearly 10%.
Concrete processing step of the present invention is as follows:
(1) raw material pre-treatment:
With biomass is raw material, pulverizes, is dried to water ratio＜8at% then, makes the material particles of particle diameter less than 2mm;
(2) Poor oxygen gas preparation:
Air imports the Poor oxygen gas producer by air compressor, the Poor oxygen gas that produces enters the gas buffer jar, the gas that the gas buffer jar comes out is divided into two-way through spinner-type flowmeter: the main road that flow is bigger enters the reactor bottom preheating, enters reactor through gas distribution grid; The less route feed bin top of flow feeds, and together enters reactor along material;
(3) magnetic stabilization fluid bed reaction:
Biological particles enters by feeding screw with Poor oxygen gas and carries out fast pyrolysis in the magnetic stabilization fluid bed bioreactor, input rate is 5-10kg/h, the regulation and control magneticstrength makes the bed material just in time be restricted in the reactor, Poor oxygen gas being mixed together of fluidized bed material and material in reactor, and the lanthanum-cerium mischmetal compound that adds material quantity 1～3at% is as catalyzer, with reduce alkali (NaOH, KOH) and salt (NaCl, KCl, Na
2CO
3, K
2CO
3) composition, reactor is heated between 450-550 ℃, and material is degraded under the high temperature anoxia condition, generates cracking steam and charcoal, and pyrolytical condition: pressure is 1～1.4kPa, fluidising air velocity 0.20-0.30m/s;
(4) product collection:
Charcoal is collected by cyclonic separator and collection charcoal case; Oil vapour in the cracking steam is collected in the oil-collecting bottle by condenser, and condenser temperature maintains-1～1 ℃.Non-condensable gas in the cracking steam is through filter compression gas tank collection storage;
(5) product is refining:
The phlegma of oil vapour is through making catalyzer with CoMo, and at pressure 9～11Mpa, behind simple hydrogenation 3～5min, distillation is handled under the temperature 300-350 ℃ of condition, and 380～450 ℃ of distillation temperatures are made bio oil.
The cracking resultant is formed by mass percentage: bio oil 60-75%; Charcoal 10-13%; Gas 12-15% (N
240-50%, CO25-35%, CO
25-10%, CH
45-10%, other 10-20%).Bio oil viscosity＞10
6MPa.s, density＞1.10, pH value＞2.5, calorific value＞33MJ/kg, water ratio＜20% (massfraction).Bio oil ultimate analysis (massfraction): C＞71.1%, H＞7.3%, O＞16.6%, N＜0.1%.
Described biomass be stalk, leaf, wood chip and or organic waste.
The invention has the beneficial effects as follows: concentrated the advantage of fluidized-bed and fixed bed, technology is simple, and treatment capacity is big, and residence time of material is short, is heated evenly, and the bio oil productive rate is up to more than 70%.Make biomass pyrolytic reaction efficiency higher, production technique is more stable.And bio oil product calorific value height, sulfur-bearing, nitrogen, chlorine, heavy metal seldom, environmental protection.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Embodiment:
The biomass of utilizing of the present invention are as raw material, adopt the technology of warm fast pyrolysis system bio oil in the magnetic stabilization fluid bed bioreactor, raw material is through pre-treatment, middle temperature fast pyrolysis, cyclonic separator gas, the solid separation, condensation of gas, obtain bio oil (process flow sheet as shown in Figure 1) after refining.Be raw material with the corn cob now, particular content of the present invention described in detail:
(1) raw material pre-treatment:
Collect corn cob, pulverizing then, dry (water ratio＜8%) are also made the material particles of particle diameter less than 2mm.
(2) Poor oxygen gas preparation:
Air imports the Poor oxygen gas producer by air compressor, and the Poor oxygen gas of generation is pressed into surge tank.The gas that comes out from the gas buffer jar is divided into two-way through spinner-type flowmeter: the main road that flow is bigger enters the reactor bottom preheating, enters reactor through gas distribution grid; The less route feed bin top of flow feeds, and together enters reactor along material.
(3) magnetic stabilization fluid bed reaction:
Material enters by feeding screw with Poor oxygen gas and carries out fast pyrolysis in the magnetic stabilization fluid bed bioreactor.Input rate is 5kg/h.Regulate magneticstrength, the bed material just in time is limited in the reactor by externally-applied magnetic field, do not escape.Poor oxygen gas mixture of fluidized bed material and material together in reactor, and add a small amount of rare earth compound as catalyzer, to reduce alkali and salt component.Reactor is added nichrome wire and is heated to 500 ℃, and material under the high temperature anoxia condition thermal destruction takes place, and generates thermo-cracking steam and charcoal.The Poor oxygen gas that enters reactor leaves reactor with resultant, tangentially enters cyclonic separator.Pyrolytical condition: pressure is 1.25kPa, fluidising air velocity 0.25m/s.
(4) product collection:
Biomass charcoal is collected by cyclonic separator and collection charcoal case; Oil vapour is collected in the oil-collecting bottle by condenser (condenser temperature maintains 0 ℃).Gaseous product process filter is removed the tar of molecular surface, uses the compression gas tank collection storage.
(5) product is refining:
Product carries out hydrogenation reaction earlier, and CoMo makes catalyzer, pressure 10Mpa, 300 ℃ of temperature, time 3min.Distill refiningly subsequently, after the about 400 ℃ of processing of controlled temperature, make bio oil.
Resultant is formed (massfraction): bio oil 75%; Charcoal 12%; Gas 13%.Bio oil viscosity＞10
6MPa.s, density 1.40, pH value 2.9, calorific value 32MJ/kg, water ratio 10%.Bio oil ultimate analysis: C content 72.1%, H content 7.6%, O content 16.8%, N content 0.05%.
Claims (4)
1. a bio oil is characterized in that: contain C＞71.1%, H＞7.3%, O＞16.6%, N＜0.1% in the bio oil by mass percentage, oil viscosity＞10
6MPa.s, density＞1.10, pH value＞2.5, water ratio＜20%.
2. method with the described bio oil of warm fast pyrolysis system claim 1 in the biomass magnetic stabilization fluid bed bioreactor is characterized in that: concrete processing step is as follows:
(1) raw material pre-treatment:
With biomass is raw material, pulverizes, is dried to water ratio＜8at% then, makes the material particles of particle diameter less than 2mm;
(2) Poor oxygen gas preparation:
Air imports the Poor oxygen gas producer by air compressor, the Poor oxygen gas that produces enters the gas buffer jar, the gas that the gas buffer jar comes out is divided into two-way through spinner-type flowmeter: the main road that flow is bigger enters the reactor bottom preheating, enters reactor through gas distribution grid; The less route feed bin top of flow feeds, and together enters reactor along material;
(3) magnetic stabilization fluid bed reaction:
Biological particles enters by feeding screw with Poor oxygen gas and carries out fast pyrolysis in the magnetic stabilization fluid bed bioreactor, input rate is 5-10kg/h, the regulation and control magneticstrength makes the bed material just in time be restricted in the reactor, Poor oxygen gas being mixed together of fluidized bed material and material in reactor, and lanthanum-cerium mischmetal compound of interpolation material quantity 1～3at% is as catalyzer, reactor is heated between 450-550 ℃, material is degraded under the high temperature anoxia condition, generate cracking steam and charcoal, pyrolytical condition: pressure is 1～1.4kPa, fluidising air velocity 0.20-0.30m/s;
(4) product collection:
Charcoal is collected by cyclonic separator and collection charcoal case; Oil vapour in the cracking steam is collected in the oil-collecting bottle by condenser, and condenser temperature maintains-1～1 ℃.Non-condensable gas in the cracking steam is through filter compression gas tank collection storage;
(5) product is refining:
The phlegma of oil vapour is through making catalyzer with CoMo, and at pressure 9～11Mpa, behind simple hydrogenation 3～5min, distillation is handled under the temperature 300-350 ℃ of condition, and 380～450 ℃ of distillation temperatures are made bio oil.
3. the method with the described bio oil of warm fast pyrolysis system claim 1 in the biomass magnetic stabilization fluid bed bioreactor according to claim 2, it is characterized in that: adopt magnetic stabilization fluid bed middle temperature fast pyrolysis system bio oil of carrying out biomass, input rate is 5-10kg/h, bed material: thin iron sand powder, particle diameter＜0.2mm.
4. the method with the described bio oil of warm fast pyrolysis system claim 1 in the biomass magnetic stabilization fluid bed bioreactor according to claim 2, it is characterized in that: described biomass are stalk, leaf, wood chip and or organic waste.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199435A (en) * | 2011-04-19 | 2011-09-28 | 安徽理工大学 | Method for preparing guaiacol-enriched biological oil by catalytic pyrolysis of biomass |
| CN101353583B (en) * | 2008-09-19 | 2012-02-22 | 河南盛润创业投资管理有限公司 | Biomass processing method |
| CN102382683A (en) * | 2010-08-31 | 2012-03-21 | 北京金骄生物质化工有限公司 | Method for preparing biomass gas from plant branches and trunks |
| CN102533340A (en) * | 2011-12-15 | 2012-07-04 | 北京金骄生物质化工有限公司 | Method utilizing waste biomasses to prepare biogas |
| TWI394829B (en) * | 2009-01-09 | 2013-05-01 | Ind Tech Res Inst | Biomass fuel generator |
| CN104755590A (en) * | 2012-10-31 | 2015-07-01 | 国际壳牌研究有限公司 | Methods and systems for processing lignin through viscosity reduction during hydrothermal digestion of cellulosic biomass solids |
| CN105602599A (en) * | 2015-10-20 | 2016-05-25 | 天津大学 | Method for preparing vehicular bio-fuel oil by using biomass all-components |
| CN115595176A (en) * | 2022-08-24 | 2023-01-13 | 宁波中金石化有限公司（Cn） | Method for reducing solid-phase product content in pyrolysis catalytic product of residual oil-hydrocracking tail oil by using modified iron sand microspheres |
-
2007
- 2007-08-15 CN CNA2007101473252A patent/CN101121895A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353583B (en) * | 2008-09-19 | 2012-02-22 | 河南盛润创业投资管理有限公司 | Biomass processing method |
| TWI394829B (en) * | 2009-01-09 | 2013-05-01 | Ind Tech Res Inst | Biomass fuel generator |
| CN102382683A (en) * | 2010-08-31 | 2012-03-21 | 北京金骄生物质化工有限公司 | Method for preparing biomass gas from plant branches and trunks |
| CN102382683B (en) * | 2010-08-31 | 2014-01-15 | 北京金骄生物质化工有限公司 | Method for preparing biomass gas from plant branches and trunks |
| CN102199435A (en) * | 2011-04-19 | 2011-09-28 | 安徽理工大学 | Method for preparing guaiacol-enriched biological oil by catalytic pyrolysis of biomass |
| CN102533340A (en) * | 2011-12-15 | 2012-07-04 | 北京金骄生物质化工有限公司 | Method utilizing waste biomasses to prepare biogas |
| CN104755590A (en) * | 2012-10-31 | 2015-07-01 | 国际壳牌研究有限公司 | Methods and systems for processing lignin through viscosity reduction during hydrothermal digestion of cellulosic biomass solids |
| CN104755590B (en) * | 2012-10-31 | 2016-08-24 | 国际壳牌研究有限公司 | Reduced by viscosity during the hydrothermal digestion of cellulose biomass solid and process the method and system of lignin |
| CN105602599A (en) * | 2015-10-20 | 2016-05-25 | 天津大学 | Method for preparing vehicular bio-fuel oil by using biomass all-components |
| CN115595176A (en) * | 2022-08-24 | 2023-01-13 | 宁波中金石化有限公司（Cn） | Method for reducing solid-phase product content in pyrolysis catalytic product of residual oil-hydrocracking tail oil by using modified iron sand microspheres |
| CN115595176B (en) * | 2022-08-24 | 2023-12-29 | 宁波中金石化有限公司 | Method for reducing content of solid-phase product in residual oil-hydrocracking tail oil pyrolysis catalytic product by utilizing modified iron sand microspheres |
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