CN101358138B - Method for improving quality of biomass oil - Google Patents
Method for improving quality of biomass oil Download PDFInfo
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- CN101358138B CN101358138B CN200810161592XA CN200810161592A CN101358138B CN 101358138 B CN101358138 B CN 101358138B CN 200810161592X A CN200810161592X A CN 200810161592XA CN 200810161592 A CN200810161592 A CN 200810161592A CN 101358138 B CN101358138 B CN 101358138B
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- oil
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- reaction
- autoclave
- biomass oil
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000002028 Biomass Substances 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000470 constituent Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims abstract description 5
- 239000012429 reaction media Substances 0.000 claims abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000012075 bio-oil Substances 0.000 claims description 29
- 239000003921 oil Substances 0.000 claims description 19
- 238000006073 displacement reaction Methods 0.000 claims description 11
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000010903 husk Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 description 11
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for improving the quality of biomass oil, which utilizes the supercritical catalytic reaction to reduce heavy constituents in the biomass oil. The biomass oil, supercritical reaction medium (ethanol or methanol) and HZSM-5 molecular sieve catalyst are poured into a high-pressure reaction kettle; after the air in the reaction kettle is replaced by N2, the reaction kettle is sealed; and under the conditions of pressure ranging between 7.5Mpa and 11Mpa, stirring speed ranging between 800 and 1200rpm and temperature ranging between 100 DEG C and 300 DEG C, reaction lasts for three to five hours. The method, which is characterized by simple technique and convenient operation, can effectively reduce the heavy constituents in the biomass oil and has the advantage of low reaction temperature.
Description
Technical field
The present invention relates to a kind of method of improving quality of biomass oil, particularly in supercritical medium, bio-oil is carried out the method that the upgrading reaction reduces heavy constituent in the bio-oil.
Background technology
Biomass are meant that by Mierocrystalline cellulose the superpolymer that hemicellulose and xylogen are formed generally based on Mierocrystalline cellulose, extensively is present in the various plant materialss, is a kind of renewable resources.Can produce bio-oil by biomass through certain chemical treatment method.Bio-oil because of its environmental friendliness, raw material sources are extensive and renewablely be subjected to extensive attention, are considered to a kind of Energy resources of alternative fossil oil.Bio-oil is a kind of mixture of complexity, contains materials such as acids, phenols and aldehydes, also contains a large amount of boiling point height, not volatile heavy constituent (the quality percentage composition reaches 30～40%).For strengthening the Practical Performance of bio-oil, must carry out the upgrading reaction to bio-oil, to reduce the heavy component content in the bio-oil.Conventional gas-solid catalysis is usually used in the upgrading of bio-oil, and temperature of reaction needs higher energy consumption generally at 400～600 ℃.
Summary of the invention
The present invention is directed to existing improving quality of biomass oil temperature of reaction problem of higher, provide a kind of at a lower temperature to the method for improving quality of biomass oil with heavy constituent in the minimizing bio-oil.
The invention provides the method for bio-oil catalysis upgrading, is to adopt molecular sieve catalyst, in supercritical medium bio-oil is carried out the upgrading reaction; Described catalyzer is HZSM-5; Described supercritical medium is ethanol or methyl alcohol.Concrete reaction method is: bio-oil, reaction medium and catalyzer are dropped in the autoclave, with the air N in the reactor
2Displacement back sealed reactor.At pressure 7.5～11MPa, stirring velocity 800～1200rpm, under 100～300 ℃, reaction 3～5h.
Bio-oil of the present invention is to be raw material with the rice husk, the high temperature pyrolysis oil under the secluding air condition, and pyrolysis temperature is 475 ℃.
The condition of upgrading reaction of the present invention is: pressure 7.5～11MPa, stirring velocity 800～1200rpm reacts 3～5h under 100～300 ℃ of temperature.
Si/Al=10～300 among the catalyzer HZSM-5 of the present invention.
The volume ratio of bio-oil of the present invention and supercritical medium is: 1:5～1:25.
The mass ratio of catalyzer of the present invention and supercritical medium is: 1:20～1:80.
The inventive method technology is simple, and is easy to operate, can effectively reduce the heavy component in the bio-oil, has the low advantage of temperature of reaction.
Embodiment
Embodiment 1 (non-supercritical condition)
5ml bio-oil and 30ml ethanol are placed autoclave, in autoclave, add 1.5gHZSM-5 (Si/Al=22) again.Logical N2 is with the air displacement in the autoclave.At pressure 7.5MPa, stirring velocity 1000rpm, 100 ℃ of reaction 3h.Analytical results shows that the heavy constituent quality percentage composition in the upgrading artifact matter oil is 37.9%.
Embodiment 2 (non-supercritical condition)
5ml bio-oil and 100ml ethanol are placed autoclave, in autoclave, add 1.5gHZSM-5 (Si/Al=22) again.Logical N
2With the air displacement in the autoclave.At pressure 7.8MPa, stirring velocity 800rpm, 218 ℃ of reaction 5h.Analytical results shows that the heavy constituent quality percentage composition in the upgrading artifact matter oil is 35.1%.
Embodiment 3 (super critical condition)
5ml bio-oil and 30ml ethanol are placed autoclave, in autoclave, add 1.5gHZSM-5 (Si/Al=22) again.Logical N
2With the air displacement in the autoclave.At pressure 10MPa, stirring velocity 1000rpm, 260 ℃ of reaction 3h.Analytical results shows that the heavy constituent quality percentage composition in the upgrading artifact matter oil is 15.3%.
Embodiment 4 (super critical condition)
5ml bio-oil and 80ml ethanol are placed autoclave, do not add catalyzer.Logical N
2With the air displacement in the autoclave.At pressure 10MPa, 1000,260 ℃ of reactions of stirring velocity 4h.Analytical results shows that the heavy constituent quality percentage composition in the upgrading artifact matter oil is 26.85%.
Embodiment 5 (super critical condition)
5ml bio-oil and 100ml ethanol are placed autoclave, in autoclave, add 1.5gHZSM-5 (Si/Al=100) again.Logical N
2With the air displacement in the autoclave.At pressure 10MPa, stirring velocity 800rpm, 260 ℃ of reaction 5h.Analytical results shows that the heavy constituent quality percentage composition in the upgrading artifact matter oil is 19.34%.
Embodiment 6 (super critical condition)
5ml bio-oil and 80ml ethanol are placed autoclave, in autoclave, add 1.5gHZSM-5 (Si/Al=300) again.Logical N
2With the air displacement in the autoclave.At pressure 11MPa, stirring velocity 1000rpm, 300 ℃ of reaction 3h.Analytical results shows that the heavy constituent quality percentage composition in the upgrading artifact matter oil is 15.14%.
Embodiment 7 (super critical condition)
5ml bio-oil and 120ml methyl alcohol are placed autoclave, in autoclave, add 1.5gHZSM-5 (Si/Al=22) again.Logical N
2With the air displacement in the autoclave.At pressure 8MPa, stirring velocity 900rpm, 250 ℃ of reaction 5h.Analytical results shows that the heavy constituent quality percentage composition in the upgrading artifact matter oil is 14.05%.
Embodiment 8 (super critical condition)
5ml bio-oil and 50ml methyl alcohol are placed autoclave, in autoclave, add 1.50gHZSM-5 (Si/Al=100) again.Logical N
2With the air displacement in the autoclave.At pressure 8MPa, stirring velocity 1000rpm, 250 ℃ of reaction 3h.Analytical results shows that the heavy constituent quality percentage composition in the upgrading artifact matter oil is 26.06%.
Embodiment 9 (super critical condition)
5ml bio-oil and 90ml methyl alcohol are placed autoclave, in autoclave, add 1.5gHZSM-5 (Si/Al=300) again.Logical N
2With the air displacement in the autoclave.Low whipping speed 800rpm, 250 ℃ of reaction 3h.Analytical results shows that the heavy constituent quality percentage composition in the upgrading artifact matter oil is 27.13%.
Claims (3)
1. the method for an improving quality of biomass oil, it is characterized in that reducing heavy constituent in the bio-oil by overcritical catalyzed reaction, bio-oil, supercritical reaction medium ethanol or methyl alcohol and HZSM-5 molecular sieve catalyst are dropped in the autoclave, with the air N in the reactor
2Displacement back sealed reactor, at pressure 7.5～11MPa, stirring velocity 800～1200rpm under 100～300 ℃ the temperature condition, reacted 3～5 hours; Described bio-oil: the volume ratio of supercritical reaction medium is: 1:5～1:25; The mass ratio of described HZSM-5 molecular sieve catalyst and supercritical reaction medium is: 1:20～1:80.
2. the method for improving quality of biomass oil according to claim 1 is characterized in that described bio-oil is is raw material with the rice husk, the high temperature pyrolysis oil under the secluding air condition, and pyrolysis temperature is 475 ℃.
3. the method for improving quality of biomass oil according to claim 1 is characterized in that Si/Al=10～300 among the described molecular sieve catalyst HZSM-5.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810161592XA CN101358138B (en) | 2008-09-23 | 2008-09-23 | Method for improving quality of biomass oil |
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| CN200810161592XA CN101358138B (en) | 2008-09-23 | 2008-09-23 | Method for improving quality of biomass oil |
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| CN101358138A CN101358138A (en) | 2009-02-04 |
| CN101358138B true CN101358138B (en) | 2011-08-24 |
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| CN200810161592XA Expired - Fee Related CN101358138B (en) | 2008-09-23 | 2008-09-23 | Method for improving quality of biomass oil |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812376B (en) * | 2010-04-20 | 2012-08-22 | 浙江大学 | Method for catalyzing, esterifying and upgrading bio-oil under microwave condition |
| CN102021048B (en) * | 2010-12-08 | 2013-08-28 | 华南农业大学 | Biomass liquefaction method in presence of coupling action of subcritical/supercritical cyclohexane and molecular sieve |
| CN103555353B (en) * | 2013-08-26 | 2016-10-05 | 福建农林大学 | A kind of method of supercritical fluid catalytic liquefaction plant material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107031A (en) * | 1976-09-16 | 1978-08-15 | Union Oil Company Of California | Hydrocracking process with reactivated catalyst |
| WO2004099115A1 (en) * | 2003-05-06 | 2004-11-18 | Coppe/Ufrj - Coordenação Dos Programas De Pós Graduação De Engenharia Da Universidade Federal Do Rio De Janeiro | Process for extraction and catalytic esterification of fatty acids found in sewage scum |
| CN101016468A (en) * | 2007-02-13 | 2007-08-15 | 中国矿业大学 | Method and device of modifying and quality increasing biomass liquefied oil under mild condition |
-
2008
- 2008-09-23 CN CN200810161592XA patent/CN101358138B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107031A (en) * | 1976-09-16 | 1978-08-15 | Union Oil Company Of California | Hydrocracking process with reactivated catalyst |
| WO2004099115A1 (en) * | 2003-05-06 | 2004-11-18 | Coppe/Ufrj - Coordenação Dos Programas De Pós Graduação De Engenharia Da Universidade Federal Do Rio De Janeiro | Process for extraction and catalytic esterification of fatty acids found in sewage scum |
| CN101016468A (en) * | 2007-02-13 | 2007-08-15 | 中国矿业大学 | Method and device of modifying and quality increasing biomass liquefied oil under mild condition |
Non-Patent Citations (1)
| Title |
|---|
| 周磊 等.生物油的组成和提质研究的进展.《化工时刊》.2007,第21卷(第6期),69-71. * |
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| CN101358138A (en) | 2009-02-04 |
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