CN102776015B - Method for improving yield of liquefied biological oil by pretreating biomass with ultrasonic waves - Google Patents
Method for improving yield of liquefied biological oil by pretreating biomass with ultrasonic waves Download PDFInfo
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- CN102776015B CN102776015B CN201210285100.4A CN201210285100A CN102776015B CN 102776015 B CN102776015 B CN 102776015B CN 201210285100 A CN201210285100 A CN 201210285100A CN 102776015 B CN102776015 B CN 102776015B
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Abstract
The invention relates to a method for improving the yield of liquefied biological oil by pretreating biomass with ultrasonic waves. According to the method, cellulose is firstly pretreated with ultrasonic waves; and then, the pretreated cellulose is liquefied at a certain temperature with certain water content for certain retention time; and finally the process steps such as separation, extraction, filtration and evaporation are carried out to obtain biological oil with high yield. Compared with the prior art, the method can remarkably improve the yield of biological oil, is simple in technology and is economical and environmental.
Description
Technical field
The invention belongs to biomass renewable energy source and derived energy chemical field, especially relate to a kind of method utilizing ultrasonic pretreatment biomass to improve liquefaction bio oil productive rate.
Background technology
Along with day by day exhausted and global constantly the warming up of fossil energy, exploitation renewable energy source is extremely urgent.Biomass are a kind of reproducible natural resourcess, and its reserves are huge.Mierocrystalline cellulose is the chief component of biomass, about account for the 40-50% of its composition.Therefore, effectively transforming Mierocrystalline cellulose becomes chemical and biofuel can solve the energy dilemma and environmental stress faced at present.The utilization ways of biomass mainly contains chemical method and biological process, and chemical method mainly contains fast pyrogenation, slow pyrolysis, hydrothermal method, evaporating method etc., and wherein hydrothermal method is considered to one of the most promising method.
Hydrothermal method take water as solvent, to produce the technology (Wu Chaowen etc. for the purpose of liquid bio oil at relatively high temperature (200-400 DEG C) and pressure (5-40MPa), Mierocrystalline cellulose hydrothermal liquefaction process under different atmosphere, East China University of Science's journal (natural science edition), 37,430-434 page).The thermochemical liquefaction of biomass is widely studied, and in order to improve the productive rate of bio oil, number acid alkaline catalysts is as H
2sO
4, HCl, H
3pO
4, HCOOH, NaOH, KOH, Ca (OH)
2, Na
2cO
3, KHCO
3, ZnCl
2, FeCl
3, FeCl
2, Rb
2cO
3, Cs
2cO
3deng being used, although these catalyzer add the DeR of cellulose surface, but do not improve cellulosic reactive behavior, bio oil productive rate improves limited.Meanwhile, these catalyzer are often serious to equipment corrosion, produce waste water and gas, contaminate environment.
Ultrasonic pretreatment is a kind of pure physical method, and processing unit is simple, without any environmental pollution.Ultrasonic effect is mainly from cavatition, and can produce the high temperature of more than 5000K and the high pressure of about 505MPa within extremely short time and minimum space, rate of temperature change is up to 10
10k/s, the shockwave that the high pressure produced when being collapsed by bubble causes and microjet, cellulosic crystalline texture is destroyed in solid-liquid system, make structure relatively fluffy, solvent is impelled to be deep into cellulose grain inside, improve the accessibility of solvent, but also can destroy in cellulosic molecule and intermolecular hydrogen bond reduction degree of crystallinity, improve reactive behavior.Mierocrystalline cellulose after ultrasonic pretreatment is used to liquefaction preparation bio oil as raw material, can obtain high bio oil productive rate, avoid the use of the corrosivess such as soda acid simultaneously under shorter time and temperature.Data shows, the method that ultrasonic pretreatment Mierocrystalline cellulose improves liquefaction bio oil productive rate also there is not yet report at present.
Summary of the invention
Object of the present invention is exactly provide a kind of productive rate significantly improving bio oil to overcome defect that above-mentioned prior art exists, and the ultrasonic pretreatment biomass that utilize of the simple and economic environmental protection of technology improve the method for liquefaction bio oil productive rate.
Object of the present invention can be achieved through the following technical solutions:
A kind of method utilizing ultrasonic pretreatment biomass to improve liquefaction bio oil productive rate, first the method utilizes ultrasonic wave to carry out pre-treatment to Mierocrystalline cellulose, then by process after Mierocrystalline cellulose in certain temperature, water-content, liquefy under the residence time, through being separated, extraction, filter, the bio oil of higher yields after the steps such as evaporation, can be obtained.
It is that Mierocrystalline cellulose and water are carried out ultrasonic pretreatment again by after allotment that ultrasonic wave carries out pre-treatment to Mierocrystalline cellulose, and destroy cellulosic hydrogen bond, cellulosic structure is destroyed, degree of crystallinity declines, and reactive behavior increases greatly, and Mierocrystalline cellulose appearance is expanded short texture.
The method specifically comprises the following steps:
(1) be 1 by weight by Mierocrystalline cellulose and water: the ratio mixing of (1-100), then to obtain for the purpose of loose fiber element, control ultrasonic power is 10W ~ 2000W, carries out ultrasonic pretreatment 5min ~ 5h by ultrasonic wave, obtains cellulosic suspension;
(2) pretreated cellulose suspension is transferred to high-temperature high-pressure reaction kettle, airtight, vacuumize, be then heated to 200 ~ 400 DEG C, keep 1-60min, then cool reactor and be cooled to room temperature, collection of biological oil production.
During collection of biological oil production, by reactor venting drive still after, transfer liquid and solid phase prod in beaker, filtration under diminished pressure, aqueous portion carries out rotary evaporation and obtains bio oil at 50 DEG C; Solid fraction acetone extract, extraction phase carries out revolving steaming process and obtains bio oil.
Compared with prior art, the present invention has the following advantages:
(1) productive rate of bio oil can be significantly improved.Mierocrystalline cellulose after ultrasonic pretreatment, bio oil productive rate can reach more than 60%, with the productive rate that can not improve 20% compared with the pretreated Mierocrystalline cellulose.
(2) avoid using catalyzer, cost-saving, reduce environmental pollution.Present method can be avoided using corrosive acid base catalysator, and process does not have waste water and gas to produce, and is beneficial to environmental protection, cost-saving.
(3) raw material is not limited to Mierocrystalline cellulose, also may extend to other biological matter kind, as maize straw, and rice husk, Pericarppium arachidis hypogaeae, straw, Cotton Stalk, various agriculture and forestry organic waste materials etc., of many uses.
(4) easy and simple to handle, there are industrial applications potentiality.Ultrasonication operation relative ease, the cellulose suspension after process is in stable condition, is beneficial to and adopts the process of continous way industrial equipments.
(5) the present invention utilizes Mierocrystalline cellulose for raw material, and adopt ultrasonic technology to carry out pre-treatment innovatively, then texturized fiber element liquefies.This method can significantly improve the productive rate of bio oil, and the simple and economic environmental protection of technology, is beneficial to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 be before and after ultrasonic pretreatment cellulosic SEM figure to photograph and picture.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
(1) ratio being 1: 10 by weight by Mierocrystalline cellulose and water mixes, and then carry out ultrasonic pretreatment 30min by ultrasonic wave to it, hyperacoustic power setting is 200W, obtains cellulosic suspension.
(2) pretreated cellulose suspension is transferred to high-temperature high-pressure reaction kettle, airtight, vacuumize, be then heated to 280 DEG C, keep 10min, then cool to room temperature.
(3) through product separation, dry, obtaining bio oil productive rate after weighing is 56.4%.
Embodiment 2
(1) ratio being 1: 20 by weight by Mierocrystalline cellulose and water mixes, and then carry out ultrasonic pretreatment 60min by ultrasonic wave to it, hyperacoustic power setting is 400W, obtains cellulosic suspension.
(2) pretreated cellulose suspension is transferred to high-temperature high-pressure reaction kettle, airtight, vacuumize, be then heated to 260 DEG C, keep 1min, then cool to room temperature.
(3) through product separation, dry, obtaining bio oil productive rate after weighing is 63.2%.
Embodiment 3
(1) ratio being 1: 75 by weight by Mierocrystalline cellulose and water mixes, and then carry out ultrasonic pretreatment 30min by ultrasonic wave to it, hyperacoustic power setting is 500W, obtains cellulosic suspension.
(2) pretreated cellulose suspension is transferred to high-temperature high-pressure reaction kettle, airtight, vacuumize, be then heated to 300 DEG C, keep 10min, then cool to room temperature.
(3) through product separation, dry, obtaining bio oil productive rate after weighing is 59.3%.
Embodiment 4
(1) ratio being 1: 25 by weight by Mierocrystalline cellulose and water mixes, and then carry out ultrasonic pretreatment 40min by ultrasonic wave to it, hyperacoustic power setting is 800W, obtains cellulosic suspension.
(2) pretreated cellulose suspension is transferred to high-temperature high-pressure reaction kettle, airtight, vacuumize, be then heated to 300 DEG C, keep 2min, then cool to room temperature.
(3) through product separation, dry, obtaining bio oil productive rate after weighing is 62.1%.
Embodiment 5
(1) ratio being 1: 50 by weight by Mierocrystalline cellulose and water mixes, and then carry out ultrasonic pretreatment 3h by ultrasonic wave to it, hyperacoustic power setting is 1000W, obtains cellulosic suspension.
(2) pretreated cellulose suspension is transferred to high-temperature high-pressure reaction kettle, airtight, vacuumize, be then heated to 300 DEG C, keep 10min, then cool to room temperature.
(3) through product separation, dry, obtaining bio oil productive rate after weighing is 60.8%.
Embodiment 6
A kind of method utilizing ultrasonic pretreatment biomass to improve liquefaction bio oil productive rate, first the method utilizes ultrasonic wave to carry out pre-treatment to Mierocrystalline cellulose, then by process after Mierocrystalline cellulose in certain temperature, water-content, liquefy under the residence time, through being separated, extraction, filter, the bio oil of higher yields after the steps such as evaporation, can be obtained.It is that Mierocrystalline cellulose and water are carried out ultrasonic pretreatment again by after allotment that ultrasonic wave carries out pre-treatment to Mierocrystalline cellulose, and destroy cellulosic hydrogen bond, cellulosic structure is destroyed, degree of crystallinity declines, and reactive behavior increases greatly, and Mierocrystalline cellulose appearance is expanded short texture.
The method specifically comprises the following steps:
(1) by Mierocrystalline cellulose and water be by weight 1: 1 ratio mixing, then to obtain for the purpose of loose fiber element, control ultrasonic power is 10W, carries out ultrasonic pretreatment 5h by ultrasonic wave, obtains cellulosic suspension;
(2) pretreated cellulose suspension is transferred to high-temperature high-pressure reaction kettle, airtight, vacuumize, be then heated to 200 DEG C, keep 60min, then cool reactor and be cooled to room temperature, collection of biological oil production.
During collection of biological oil production, by reactor venting drive still after, transfer liquid and solid phase prod in beaker, filtration under diminished pressure, aqueous portion carries out rotary evaporation and obtains bio oil at 50 DEG C; Solid fraction acetone extract, extraction phase carries out revolving steaming process and obtains bio oil.
Embodiment 7
A kind of method utilizing ultrasonic pretreatment biomass to improve liquefaction bio oil productive rate, first the method utilizes ultrasonic wave to carry out pre-treatment to Mierocrystalline cellulose, then by process after Mierocrystalline cellulose in certain temperature, water-content, liquefy under the residence time, through being separated, extraction, filter, the bio oil of higher yields after the steps such as evaporation, can be obtained.It is that Mierocrystalline cellulose and water are carried out ultrasonic pretreatment again by after allotment that ultrasonic wave carries out pre-treatment to Mierocrystalline cellulose, and destroy cellulosic hydrogen bond, cellulosic structure is destroyed, degree of crystallinity declines, and reactive behavior increases greatly, and Mierocrystalline cellulose appearance is expanded short texture.
The method specifically comprises the following steps:
(1) by Mierocrystalline cellulose and water be by weight 1: 100 ratio mixing, then to obtain for the purpose of loose fiber element, control ultrasonic power is 2000W, carries out ultrasonic pretreatment 5min by ultrasonic wave, obtains cellulosic suspension;
(2) pretreated cellulose suspension is transferred to high-temperature high-pressure reaction kettle, airtight, vacuumize, be then heated to 400 DEG C, keep 5min, then cool reactor and be cooled to room temperature, collection of biological oil production.
During collection of biological oil production, by reactor venting drive still after, transfer liquid and solid phase prod in beaker, filtration under diminished pressure, aqueous portion carries out rotary evaporation and obtains bio oil at 50 DEG C; Solid fraction acetone extract, extraction phase carries out revolving steaming process and obtains bio oil.
Claims (2)
1. the method utilizing ultrasonic pretreatment biomass to improve liquefaction bio oil productive rate, it is characterized in that, first the method utilizes ultrasonic wave to carry out pre-treatment to Mierocrystalline cellulose, then by process after Mierocrystalline cellulose in certain temperature, water-content, liquefy under the residence time, through being separated, extraction, filter, the bio oil of higher yields can be obtained after evaporation step, it is that Mierocrystalline cellulose and water are carried out ultrasonic pretreatment again by after allotment that ultrasonic wave carries out pre-treatment to Mierocrystalline cellulose, destroy cellulosic hydrogen bond, cellulosic structure is destroyed, degree of crystallinity declines, reactive behavior increases greatly, Mierocrystalline cellulose appearance is expanded short texture,
The method specifically comprises the following steps:
(1) by Mierocrystalline cellulose and water by weight be 1:(1-100) ratio mix, then to obtain for the purpose of loose fiber element, control ultrasonic power is 10W ~ 2000W, carries out ultrasonic pretreatment 5min ~ 5h by ultrasonic wave, obtains cellulosic suspension;
(2) pretreated cellulose suspension is transferred to high-temperature high-pressure reaction kettle, airtight, vacuumize, be then heated to 200 ~ 400 DEG C, keep 1-60min, then cool reactor and be cooled to room temperature, collection of biological oil production.
2. a kind of method utilizing ultrasonic pretreatment biomass to improve liquefaction bio oil productive rate according to claim 1, it is characterized in that, during collection of biological oil production, after still is left in reactor venting, transfer liquid and solid phase prod are in beaker, filtration under diminished pressure, aqueous portion carries out rotary evaporation and obtains bio oil at 50 DEG C; Solid fraction acetone extract, extraction phase carries out revolving steaming process and obtains bio oil.
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| CN103450920A (en) * | 2013-09-13 | 2013-12-18 | 中国农业大学 | Method for increasing heavy oil yield by treating biological crude oil with ultrasonic wave |
| DE102022100746A1 (en) * | 2022-01-13 | 2023-07-13 | HAGO Druck und Medien GmbH | Process for the production of hydrogen from biomass using SCWG |
| CN114989853B (en) * | 2022-05-17 | 2023-07-25 | 胡进 | Pretreatment method for improving yield of liquefied bio-oil prepared from biomass material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101012387A (en) * | 2007-02-01 | 2007-08-08 | 淮北中润生物能源技术开发有限公司 | Technique for manufacturing liquid fuel from highly effective cellulose biomass |
| CN101199944A (en) * | 2007-11-23 | 2008-06-18 | 淮北中润生物能源技术开发有限公司 | Cellulose biomimetic catalysis hydrolysis system and application in liquid fuel production thereof |
| CN102266864A (en) * | 2011-07-01 | 2011-12-07 | 中国科学院过程工程研究所 | Method for thermal decomposition refining and grading directional transformation of biomasses |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101012387A (en) * | 2007-02-01 | 2007-08-08 | 淮北中润生物能源技术开发有限公司 | Technique for manufacturing liquid fuel from highly effective cellulose biomass |
| CN101199944A (en) * | 2007-11-23 | 2008-06-18 | 淮北中润生物能源技术开发有限公司 | Cellulose biomimetic catalysis hydrolysis system and application in liquid fuel production thereof |
| CN102266864A (en) * | 2011-07-01 | 2011-12-07 | 中国科学院过程工程研究所 | Method for thermal decomposition refining and grading directional transformation of biomasses |
Non-Patent Citations (1)
| Title |
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| 李为民 等.生物质直接液化工艺.《现代能源化工技术》.化学工业出版社,2011,第98-99,102页. * |
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Effective date of registration: 20171114 Address after: 200444, building 1, building 2, No. 511, Lian Shan Road, Shanghai, Baoshan District, Patentee after: Shanghai Li Sheng Nano Technology Co., Ltd. Address before: 200240 Dongchuan Road, Shanghai, No. 800, No. Patentee before: Shanghai Jiao Tong University |
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