CN102226118B - Biomass fluid fuel and preparation method thereof - Google Patents
Biomass fluid fuel and preparation method thereof Download PDFInfo
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- CN102226118B CN102226118B CN201110125087.1A CN201110125087A CN102226118B CN 102226118 B CN102226118 B CN 102226118B CN 201110125087 A CN201110125087 A CN 201110125087A CN 102226118 B CN102226118 B CN 102226118B
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/322—Coal-oil suspensions
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Abstract
The invention provides a biomass fluid fuel which comprises biomass particles and fuel assistants dispersed in a liquid fuel medium, wherein the particle size of the biomass particles is less than or equal to 150 micrometers or so, preferably less than or equal to 120 micrometers or so, and more preferably less than or equal to 100 micrometers or so; the weight ratio of biomass particles to liquid fuel medium is 1:10-1:1, preferably 1:7-1:1, and most preferably 1:5-1:1; and the total content of the fuel assistants on the basis of the weight of the biomass fluid fuel is 0.5-3.0 wt%, preferably 0.8-2.0 wt%, and more preferably 0.9-1.5 wt%. Besides, the invention also provides a preparation method of the biomass fluid fuel.
Description
Technical field
The present invention relates to the further development and utilization to biomass material, particularly biomass waste, be specifically related to biomass fluid fuel and preparation method thereof, wherein in described preparation method, utilize physics and/or thermochemical method that biomass raw material particle is converted into biomass fluid fuel.
Background technology
Under the industrial background of China, have a large amount of biomass wastes, concrete example, as bagasse, vinasse slag, manioc waste, straw, straw, beans stalk, cotton stalk, cornstalk, corn cob, fallen leaves and wood chip etc., contains a large amount of macromolecular substance that can further utilize conventionally as xylogen, Mierocrystalline cellulose, hemicellulose and starch etc. in these biomass wastes.In recent years, under the overall background of green low-carbon, the further development and utilization of these biomass wastes is more and more received publicity.
Research shows, the macromolecular substance in biomass material can be decomposed to form bio-oil, charcoal and inflammable gas as heats such as xylogen, Mierocrystalline cellulose, hemicellulose and starch, and the ratio regular meeting of these products changed with temperature, pressure and reaction times.Biomass pyrolytic and biomass carbonization are exactly the thermal chemical reaction based on above-mentioned principle, wherein can change the ratio between formed various product by controlling the condition of thermal chemical reaction.Therefore, thermochemical method is a kind of effective way of utilizing biomass material.
But also there are some problems in simple thermochemical method, for example, the production cost of bio-oil is conventionally than mineral innage, and, bio-oil can not be directly used in existing power-equipment, this is because bio-oil is the hydrocarbon polymer of the equal less stable of physics and chemistry character mostly, must could apply through modification and/or refinement treatment.
Fluid fuel refers to that Flammable Solid Class 4.1 being ground in fluid medium to refinement forms the fluid that contains small solid particulate, then adds wherein dispersion agent and/or stablizer to form stable monophasic fluid, and common example is as coal water slurry or coal oil mixture.Research shows, after the Flammable Solid Class 4.1 such as coal, refinery coke, biological mud are ground to thinning processing in diesel oil or water or other fluid medium, can obtain the fluid fuel of good fluidity, this fluid fuel can be used as efficiently and burns through corresponding burner for oil fuel.
Thought based on fluid fuel, the present invention proposes the concept of biomass fluid fuel, this is a kind of fluid fuel based on biomass raw material particle, specifically by physics and/or thermochemical method, biomass material is formed to biomass fluid fuel as biomass waste particle is distributed in liquid fuel medium.
Therefore, what biomass fluid fuel of the present invention had a fluid fuel is convenient to transportation, use and efficiency of combustion advantages of higher, thereby provides new thinking as the development and application of biomass waste for solid biologic raw material.
Summary of the invention
The invention provides a kind of biomass fluid fuel, this biomass fluid fuel comprises biomass raw material particle and the fuel auxiliary agent being scattered in liquid fuel medium, the granularity of wherein said biomass raw material particle is less than or equal to approximately 150 microns, preferably be less than or equal to approximately 120 microns, be more preferably less than or equal approximately 100 microns, the weight ratio of described biomass raw material particle and described liquid fuel medium is 1: 10 to 1: 1, be preferably 1: 7 to 1: 1, most preferably be 1: 5 to 1: 1, based on described biomass fluid fuel weight, count 0.5-3.0wt% with the total content of described fuel auxiliary agent, be preferably 0.8-2.0wt%, 0.9-1.5wt% more preferably.
The present invention also provides the method for the described biomass fluid fuel of preparation, and the method comprises the steps:
Crushed biomass raw material also sieves, with obtain granularity be less than or equal to approximately 150 microns, be preferably less than or equal to approximately 120 microns, be more preferably less than or equal the biomass raw material particle of approximately 100 microns;
Make described biomass raw material particle and liquid fuel medium be mixed to form crude mixture, the weight ratio of wherein said biomass raw material particle and described liquid fuel medium is 1: 10 to 1: 1, is preferably 1: 7 to 1: 1, most preferably is 1: 5 to 1: 1;
Make described crude mixture homogenizing and add wherein fuel auxiliary agent, the total content of wherein said fuel auxiliary agent is counted 0.5-3.0wt% based on described biomass fluid fuel weight, be preferably 0.8-2.0wt%, 0.9-1.5wt% more preferably, wherein utilize high speed shear emulsifying device to carry out homogenizing, using and obtain homogeneous mixture as biomass fluid fuel.
According to the present invention, described biomass material is generally biomass waste, is specifically selected from bagasse, vinasse slag, manioc waste, straw, straw, beans stalk, cotton stalk, cornstalk, corn cob, fallen leaves and wood chip etc.Therefore, for the present invention, the source of described biomass material is still very abundant.
According to the present invention, described liquid fuel medium can be common any suitable liquid fuel, the preferred cheap not volatile liquid fuel of price comparison, be specifically as follows not volatile oily liquid fuel as heavy oil and coal tar and heavy oil component and coal tar component, wherein said heavy oil component is as heavy oil lighting end, described coal tar component, as naphtalene oil, washing oil, carbolineum and anthracene oil, is preferably used carbolineum and/or washing oil as described liquid fuel medium.
According to the present invention, described fuel auxiliary agent can be the conventional any suitable fuel auxiliary agent in this area, object is that dispersiveness, mobility, stability, oxidation-resistance and the incendivity in order to make described biomass fluid fuel is better, be specifically as follows dispersion agent, stablizer, antioxidant, pour point depressant and ignition dope, more specifically, dispersion agent can be sodium lignosulfonate, stablizer can be quaternary ammonium salt, antioxidant can be 2,6-ditertbutylparacresol, pour point depressant can be polyacrylic ester, and ignition dope can be carbonoxide acid esters.All these fuel auxiliary agents can be used alone or in combination, in any case and use, the total content of described fuel auxiliary agent in described biomass fluid fuel all as described above, based on described biomass fluid fuel weight, count 0.5-3.0wt%, be preferably 0.8-2.0wt%, more preferably 0.9-1.5wt%.
According to the present invention, described biomass material is generally through pulverizing and screening is processed and obtained granularity and be less than or equal to approximately 150 microns (approximately 100 orders), be preferably less than or equal to approximately 120 microns (approximately 120 orders), be more preferably less than or equal the biomass raw material particle of approximately 100 microns (approximately 150 orders), pulverize generally by mechanical means and carry out as crusher or pulverizer, screening utilizes standard sieve to carry out, to obtain the biomass raw material particle of needed specified particle size scope.
According to the present invention, if described biomass material water content is excessive, generally be dried in advance described biomass material, such as drying machines such as utilizing whirlwind, be dried, preferably be dried to water-content lower than 15wt%, more preferably less than 10wt%, further preferably lower than 5wt%, thereby be beneficial to the follow-up pulverizing of described biomass material and screening processing.
According to the present invention, for making the high speed shear emulsifying device of described crude mixture homogenizing, it can be the conventional any suitable high speed shear emulsifying device in this area, can be for example colloidal mill or high speed pulverizer, this equipment makes it refinement and/or emulsification by the further shearing-crushing of crude mixture of described biological particles and described liquid fuel medium, and then makes it homogenizing.
According to the present invention, for the stronger biomass material biomass material that for example fibre content is higher of toughness as vinasse slag, because this biolobic material raw material is not easy Mechanical Crushing conventionally to very thin granularity, therefore before making described crude mixture homogenizing, generally also make described crude mixture experience carbonizing treatment, be beneficial to further broken described biomass raw material particle.
Particularly, after carbonizing treatment, biomass raw material particle causes toughness variation and physical strength to reduce because carbonization becomes fragile, thereby is easy to further be broken into thinner particle under shear action.Described carburizing reagent is generally carried out under high-speed stirring condition, and therefore, the biomass raw material particle in described crude mixture just can realize to a certain extent further refinement in carbonization process.
In addition, in carbonation reaction, also produce bio-oil, wherein under high-speed stirring and strong convection effect, mass transfer and heat transfer process have been strengthened, the bio-oil producing can be distributed to becomes liquid fuel medium in described crude mixture, further reduce the solid content of fluid fuel, be beneficial to the further homogenizing of described fluid fuel, thereby can obtain the more biomass fluid fuel of high-quality.
According to the present invention, the carbonizing treatment of described crude mixture is under agitation carried out conventionally under normal pressure and relative low temperature condition, and the carburizing reagent time is generally shorter, particularly, described temperature can be 200-300 ℃, be preferably 215-290 ℃, 250-280 ℃ more preferably, the described carburizing reagent time can be 1-10 minute, be preferably 2-7 minute, 3-5 minute more preferably, and now can be short as far as possible by controlling the carburizing reagent time, make biomass that incomplete carbonization occur and form semicoke material and part biological matter oil, due to the toughness of described semicoke material, variation and physical strength reduce, therefore, can realize the described biological particles of further fragmentation and then improve the object of described biomass fluid fuel quality.
According to the present invention, in described carbonation reaction, also produce some biomass light constituents, can collect these biomass light constituents as industrial chemicals or fuel, for example this biomass light constituent can be used as fuel and provides heat for described carbonization process, thereby it is self-supporting to realize at least partly the heat of described carbonization process.
According to the present invention, described crude mixture can carry out carbonization in existing any suitable reactor in the prior art, but is preferably reactor class reactor, more preferably with the stainless steel cauldron of stirring rake.
Preferably, according to the present invention, make described crude mixture under atmospheric pressure in the stainless steel cauldron with stirring rake, carry out carbonization, wherein under agitation condition, be heated to 215-290 ℃, be preferably heated to 250-280 ℃, the rotating speed of stirring rake is 500-1500 rev/min, be preferably 800-1350 rev/min, the residence time of more preferably 1000-1200 rev/min, and described crude mixture in described reactor is 1-10 minute, be preferably 2-7 minute, more preferably 3-5 minute.
According to the present invention, described biomass fluid fuel can utilize biomass material widely, particularly can utilize a large amount of biomass wastes, so just can " turn waste into wealth ", be beneficial to further developing of biomass energy, and the preparation technology of described biomass fluid fuel is relatively simple, the equipment using is also the common equipment of prior art, therefore, easily carrying out industry amplifies, can produce continuously, possesses good industrialization prospect, and then provide good in selecting fuel for fuel market, for example can be used for modern boiler, Industrial Stoves, with steam turbine etc.
Accompanying drawing explanation
Fig. 1 is the schema of a kind of embodiment of the method for being prepared biomass fluid fuel by biomass material of the present invention; With
Fig. 2 is the schema of the another embodiment of the method for being prepared biomass fluid fuel by biomass material of the present invention, wherein on the basis of the embodiment of Fig. 1, further combines carburising step.
Embodiment
With reference to Fig. 1, the method for preparing biomass fluid fuel by biomass material of the present invention can be carried out according to following process:
In drying machine, biomass material is dried to water-content lower than 10wt% as manioc waste, then respectively through crusher and pulverizer carry out coarse reduction and Crushing of Ultrafine and through blower fan send into sifter for example 150 object standard sieves sieve and obtain the biomass raw material particle that granularity is less than or equal to approximately 100 microns;
After described biomass raw material particle is collected with liquid fuel medium from container for storing liquid for example carbolineum for example agitation mixer in be uniformly mixed to scale formation crude mixture at 1: 3; With
Add high speed shear emulsifying device as carried out homogenizing in colloidal mill or high speed pulverizer described crude mixture, and add wherein such as dispersion agent and/or stablizer etc. of fuel auxiliary agent, the total content of wherein said fuel auxiliary agent is counted 0.9-1.5wt% based on described biomass fluid fuel weight, the homogeneous mixture obtaining after homogenizing is biomass fluid fuel, and the biomass fluid fuel obtaining is stored and transports in accumulating tank.
With reference to Fig. 2, wherein on the basis of the embodiment of Fig. 1, further combine carburising step, particularly:
Wherein biological particles dry and that screening biomass material obtains (has been carried out to coarse reduction operation at this, this is owing to combining carburising step below, therefore pulverizing requires lower slightly) form after crude mixture as carbolineum for example agitation mixer in is uniformly mixed to scale at 1: 3 with liquid fuel medium, described crude mixture is added in the stainless steel cauldron with stirring rake of carbonization reactor, described reactor can be the normal-pressure reaction kettle with steam jacket, wherein under agitation condition, be heated to for example 250-280 ℃, the rotating speed of stirring rake is for example 1000-1300 rev/min, with the residence time of described crude mixture in described reactor be for example 1-5 minute,
Then, as above for as described in Fig. 1, make the reaction mixture of extraction from described reactor carry out homogenizing and add fuel auxiliary agent, to obtain final biomass fluid fuel, at this, the biomass light constituent obtaining in carbonization process can be used for for described stainless steel cauldron provides heat, specifically can be used as the fuel of heating boiler to produce for heating the steam of described stainless steel cauldron, thereby can realize at least partly the heat self-sufficiency of carbonization process of the present invention.
By following embodiment, further describe method of the present invention, but described embodiment is not used in and limits the scope of the invention.
Embodiment
Embodiment 1 utilizes manioc waste to prepare biomass fluid fuel
It is below 8wt% that manioc waste is dried to water-content, uses pulverizer to carry out fragmentation to described manioc waste, sieves and obtain 400 grams of the following biomass raw material particle of 170 orders (90 microns) after fragmentation; Described biomass raw material particle and liquid fuel medium carbolineum are mixed to form to crude mixture by the weight ratio of 4: 6; Described crude mixture is joined and in colloidal mill, carries out homogenizing processing, add wherein nonionic surface active agent as fuel auxiliary agent simultaneously, described nonionogenic tenside is Gemini quaternary ammonium salt 1231, in this as stablizer, use, add-on is 10 grams, obtains biomass fluid fuel after homogenizing.
The stability test of described biomass fluid fuel show its in 24 hours without layering with do not produce hard-caked sediment, further performance test shows that described biomass fluid fuel has higher thermal value and good fluidity, its performance perameter is described in table 1 below.
The performance perameter of the biomass fluid fuel that table 1, embodiment 1 obtain
| Performance perameter | Numerical value |
| Solid content (wt%) | 40 |
| Density (kg/l) | 1.18 |
| Kinematic viscosity η (20 ℃, shearing rate 100s -1)MPa·s | 570 |
| Calorific value Q (kcal/kg) | 6917 |
| Ash amount (wt%) after burning | 0.39 |
Embodiment 2 utilizes vinasse slag to prepare biomass fluid fuel
It is below 6wt% that vinasse slag is dried to water-content, uses pulverizer to carry out fragmentation to described vinasse slag, sieves and obtain 200 grams of the following biomass raw material particle of 100 orders (150 microns) after fragmentation; Described biomass raw material particle and liquid fuel medium carbolineum are mixed to form to crude mixture by the weight ratio of 1: 1; It is in the normal pressure stainless steel cauldron with steam jacket of 2 liters that described crude mixture is joined to volume, wherein under agitation condition, be heated to for example 250-280 ℃, the rotating speed of stirring rake is 1000 revs/min, and the carburizing reagent time be 5 minutes, to obtain reaction mixture; Described reaction mixture is carried out in colloidal mill to homogenizing processing, add wherein cationic surfactant as fuel auxiliary agent, described cats product, for class of department 80, is used in this as stablizer simultaneously, add-on is 3 grams, obtains biomass fluid fuel after homogenizing.
The stability test of described biomass fluid fuel show its in 24 hours without layering with do not produce hard-caked sediment, further performance test shows that described biomass fluid fuel has higher thermal value and good fluidity, its performance perameter is described in table 2 below.
The performance perameter of the biomass fluid fuel that table 2, embodiment 2 obtain
| Performance perameter | Numerical value |
| Solid particulate granularity (μ m) | 28 |
| Solid content (wt%) | 34.6 |
| Density (kg/l) | 1.24 |
| Kinematic viscosity η (50 ℃, shearing rate 100s -1)MPa·s | 860 |
| Calorific value Q (kcal/kg) | 8715 |
| Ash amount (wt%) after burning | 4.48 |
Claims (26)
1. a biomass fluid fuel, this biomass fluid fuel comprises biomass raw material particle and the fuel auxiliary agent being scattered in liquid fuel medium, the granularity of wherein said biomass raw material particle is less than or equal to 150 microns, the weight ratio of described biomass raw material particle and described liquid fuel medium is 1:3 to 1:1, the total content of described fuel auxiliary agent is counted 0.5-3.0wt% based on described biomass fluid fuel weight, and described liquid fuel medium is selected from heavy oil, coal tar, heavy oil component and coal tar component.
2. the biomass fluid fuel of claim 1, the particle diameter of wherein said biomass raw material particle is less than or equal to 120 microns, the weight ratio of described biomass raw material particle and described liquid fuel medium is 1:1, and the total content of described fuel auxiliary agent is counted 0.8-2.0wt% based on described biomass fluid fuel weight.
3. the biomass fluid fuel of claim 2, the particle diameter of wherein said biomass raw material particle is less than or equal to 100 microns, and the total content of described fuel auxiliary agent is counted 0.9-1.5wt% based on described biomass fluid fuel weight.
4. the biomass fluid fuel of claim 1-3 any one, wherein said biomass material is the biomass waste that is selected from bagasse, vinasse slag, manioc waste, straw, straw, beans stalk, cotton stalk, cornstalk, corn cob, fallen leaves and wood chip.
5. the biomass fluid fuel of claim 1-3 any one, wherein said liquid fuel medium is selected from carbolineum and washing oil.
6. the biomass fluid fuel of claim 1-3 any one, wherein said fuel auxiliary agent is selected from dispersion agent, stablizer, antioxidant, pour point depressant and ignition dope.
7. a method of preparing biomass fluid fuel, the method comprises the steps:
Crushed biomass raw material also sieves, and is less than or equal to the biomass raw material particle of 150 microns to obtain granularity;
Make described biomass raw material particle and liquid fuel medium be mixed to form crude mixture, the weight ratio of wherein said biomass raw material particle and described liquid fuel medium is 1:3 to 1:1, and described liquid fuel medium is selected from heavy oil, coal tar, heavy oil component and coal tar component;
Make described crude mixture homogenizing and add wherein fuel auxiliary agent, the total content of wherein said fuel auxiliary agent is counted 0.5-3.0wt% based on described biomass fluid fuel weight, wherein utilize high speed shear emulsifying device to carry out homogenizing, using and obtain homogeneous mixture as biomass fluid fuel.
8. the method for claim 7, wherein in pulverizing and sieving step, obtain the biomass raw material particle that granularity is less than or equal to 120 microns, weight ratio at biomass raw material particle described in mixing step and described liquid fuel medium is 1:1, and the total content of the fuel auxiliary agent adding in homogenization step is counted 0.8-2.0wt% based on described biomass fluid fuel weight.
9. the method for claim 8, wherein in pulverizing and sieving step, obtain the biomass raw material particle that granularity is less than or equal to 100 microns, and the total content of the fuel auxiliary agent adding in homogenization step is counted 0.9-1.5wt% based on described biomass fluid fuel weight.
10. the method for claim 7-9 any one, wherein said biomass material is the biomass waste that is selected from bagasse, vinasse slag, manioc waste, straw, straw, beans stalk, cotton stalk, cornstalk, corn cob, fallen leaves and wood chip.
The method of 11. claim 7-9 any one, wherein said liquid fuel medium is selected from carbolineum and washing oil.
The method of 12. claim 7-9 any one, wherein said fuel auxiliary agent is selected from dispersion agent, stablizer, antioxidant, pour point depressant and ignition dope.
The method of 13. claim 7-9 any one was wherein dried in advance water-content lower than 15wt% by described biomass material before pulverizing and sieving.
The method of 14. claims 13 was wherein dried in advance water-content lower than 10wt% by described biomass material before pulverizing and sieving.
The method of 15. claims 14 was wherein dried in advance water-content lower than 5wt% by described biomass material before pulverizing and sieving.
The method of 16. claim 7-9 any one, wherein for making the high speed shear emulsifying device of described crude mixture homogenizing be selected from colloidal mill and high speed pulverizer.
The method of 17. claim 7-9 any one, for the higher biomass material of fibre content, wherein also be included in and make to make described crude mixture under atmospheric pressure in the stainless steel cauldron with stirring rake, carry out the step of carbonization before described crude mixture homogenizing, wherein under agitation condition, be heated to 215-290 ℃, and the rotating speed of stirring rake is 500-1500 rev/min.
The method of 18. claims 17 is wherein heated to 250-280 ℃ in carburising step under agitation condition, and the rotating speed of stirring rake is 800-1350 rev/min.
The method of 19. claims 17, the residence time of wherein said crude mixture in described reactor is 1-10 minute.
The method of 20. claims 18, the residence time of wherein said crude mixture in described reactor is 1-10 minute.
The method of 21. claims 17, the residence time of wherein said crude mixture in described reactor is 3-5 minute.
The method of 22. claims 18, the residence time of wherein said crude mixture in described reactor is 3-5 minute.
The method of 23. claims 19, also comprises and collects the biomass light constituent producing in carbonization process, and this biomass light constituent provides heat as fuel for described carbonization process.
The method of 24. claims 20, also comprises and collects the biomass light constituent producing in carbonization process, and this biomass light constituent provides heat as fuel for described carbonization process.
The method of 25. claims 21, also comprises and collects the biomass light constituent producing in carbonization process, and this biomass light constituent provides heat as fuel for described carbonization process.
The method of 26. claims 22, also comprises and collects the biomass light constituent producing in carbonization process, and this biomass light constituent provides heat as fuel for described carbonization process.
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| CN102226118B (en) * | 2011-05-16 | 2014-03-19 | 科威国际技术转移有限公司 | Biomass fluid fuel and preparation method thereof |
| CN102703146A (en) * | 2012-06-19 | 2012-10-03 | 贵州联和能源清洁燃料有限公司 | Low-sulfur low-ash biomass anthracite coal water slurry and preparation method thereof |
| WO2016101120A1 (en) * | 2014-12-23 | 2016-06-30 | Rhodia Operations | Slurry suspension comprising torrefied wood particles |
| EP3237586A4 (en) * | 2014-12-23 | 2018-06-27 | Rhodia Operations | Slurry suspension comprising torrefied wood particles |
| US10155913B2 (en) | 2016-04-20 | 2018-12-18 | Next Alternative Inc. | Systems and methods for manufacturing emulsified fuel |
| CN106833777B (en) * | 2017-03-23 | 2019-10-29 | 新奥科技发展有限公司 | A kind of method and device preparing water coke slurry with semicoke |
| CN106967469B (en) * | 2017-04-27 | 2020-05-19 | 武汉凯迪工程技术研究总院有限公司 | High-concentration biomass slurry and preparation method and application thereof |
| CN108264944B (en) * | 2017-12-21 | 2019-07-02 | 北京三聚环保新材料股份有限公司 | A method of improving biomass and coal solid content in the oil |
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