CN102250158B - Method for preparing levoglucosenone - Google Patents
Method for preparing levoglucosenone Download PDFInfo
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- CN102250158B CN102250158B CN201110134871.9A CN201110134871A CN102250158B CN 102250158 B CN102250158 B CN 102250158B CN 201110134871 A CN201110134871 A CN 201110134871A CN 102250158 B CN102250158 B CN 102250158B
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Abstract
The invention discloses a method for preparing levoglucosenone, which comprises the following steps: enabling biomass to be in contact with acid, wherein the acid is solid acid, sulfuric acid or a mixture of sulfuric acid and other liquid acid; and carrying out pyrolysis at 200-380 DEG C, collecting the liquid, and separating out levoglucosenone. The biomass material and the acid catalyst in the method are common, easy to acquire and low in cost; the pyrolysis temperature is low, and the product yield can be improved; and the corrosion and pollution caused by the acid can be effectively reduced. Thus, the method for preparing levoglucosenone is economic and effective.
Description
Technical field
The present invention relates to organism preparation field, particularly a kind of method of levoglucosenone of being prepared by acid catalysis pyrolysis by biomass.
Background technology
Biomass refer to the various organisms that utilize atmosphere, water, soil etc. to produce by photosynthesis, and it comprises all plants, microorganism and take animal that plant, microorganism be food and the waste of production thereof.Day by day serious along with the consumption of the fossil energy such as coal, oil in global range and problem of environmental pollution, it is more and more urgent that people find a kind of demand reproducible, clear energy sources.Than fossil energy, biomass resource has distribute wide, large, pollution-free, the reproducible feature of total amount.Biomass resource is the unique continuable source of organic carbon, is also unique renewable resources that can be converted into liquid fuel.So biomass resource more and more receives people's concern.
Biomass pyrolytic especially fast pyrogenation can obtain liquid fuel and the chemical of high added value, is considered to utilize one of efficient manner of biomass energy.Selective catalysis pyrolysis is under the condition of catalyzer, to make biomass directional thermal decomposition adding, thereby improves the productive rate of one or more products.
Levoglucosenone is a kind of α; β-unsaturated cyclic ketones; its structure is unique; it is a kind of important chiral raw material; can be used for synthetic carbohydrate and non-carbohydrate derivative; be widely used in the preparation and organic synthesis of chiral adjuvant, but the current production that also there is no mass-producing, and commercially available price is very expensive.It is Mierocrystalline cellulose that traditional method is prepared the raw material that levoglucosenone mainly uses, and process is used phosphate impregnation, filters, and dries, and carries out fast pyrogenation on different pyrolysis installations.The amount of best phosphate impregnation is about 3% left and right, and its levoglucosenone productive rate is in 6% left and right.But this method is raw materials used higher than biomass price, and do not have effective means to reduce corrodibility and the contaminative of acid catalyst.Therefore be badly in need of finding a kind of raw material and catalyzer price lower, productive rate is higher, and the method that can reduce contaminative is prepared levoglucosenone.
Summary of the invention
The technical problem to be solved in the present invention, for for prepare the low shortcoming of method productive rate of levoglucosenone in prior art with Mierocrystalline cellulose, provides a kind of method of preparing levoglucosenone.
A kind of method of preparing levoglucosenone provided by the invention, comprises the following steps:
1) biomass are contacted with acid, described acid is the mixture of solid acid, sulfuric acid or sulfuric acid and other liquid acid;
2) in temperature, be at 200～380 ℃, to carry out pyrolysis, collect liquid, isolate levoglucosenone.
The method of preparing levoglucosenone provided by the present invention, its principle is: the Mierocrystalline cellulose in biomass issues raw molecular breakdown at mixture or the solid acid catalysis of sulfuric acid or sulfuric acid and other liquid acid, and follow dehydration reaction, generate the bio oil that contains levoglucosenone.The bio oil obtaining is neutralized with alkali lye, then use dichloromethane extraction, revolve and boil off organic solvent and lower boiling component, it is 70-80 ℃ that boiling point is controlled in last underpressure distillation, i.e. separation obtains levoglucosenone.
The present invention selects biomass as raw material, because the difference in Mierocrystalline cellulose crystallizing field and unsetting district can increase itself and the site that contacts of acid catalyst, thereby can be better and catalyzer as effect of sulfuric acid, improve products collection efficiency; Selecting mixture or the solid acid of sulfuric acid or sulfuric acid and other liquid acid is that catalyzer can activate dehydration reaction greatly, makes pyrolysis just can generate easily levoglucosenone at low temperature, thereby reduces pyrolysis temperature.
According to the present invention, described biomass can be converted products, forest and forest tree castoff, farm crop and agricultural waste material, the waterplant of Mierocrystalline cellulose and rich cellulose.
As preferably, step 1 can, by biomass acid by biomass dip treating in vitriolated aq acid soln, then be carried out drying and processing; Or use solid acid to mix with biomass; Or adopt other pyrolysis that can make biomass to be subject to acid catalyzed processing mode.
The mixture of sulfuric acid of the present invention and other liquid acid, other liquid acid are preferably hydrochloric acid, the Lewis acid except chromium chloride, boric acid, organic acid.
Lewis acid refers to electron acceptor, forms the centrosome of coordinate bond.Common Lewis acid has the fluoroform sulphonate of aluminum chloride, iron(ic) chloride, boron trifluoride, columbium pentachloride and lanthanon.As preferably, Lewis acid of the present invention is iron(ic) chloride or zinc chloride.
In a specific embodiment of the present invention, the ratio of biomass and solution can be 1g: 0.1ml～1g: 1L, acid concentration can be 0.001～18M.
According to an embodiment of the invention, suitable proportion provided by the present invention is 1g biomass while being immersed in 10ml acid solution, and preferred sulfuric acid dipping concentration is 0.01～3M,
As preferably, a kind of embodiment of the method for the invention is for being used solid acid or acid being loaded on carrier and mixed with biomass.Utilize cellular solid as carrier, acid is loaded on carrier and biomass effect again, or selecting catalyst is solid acid, all can effectively reduce sour corrodibility and contaminative.
Solid acid refers to the solid that can provide proton or accept electron pair, is the class important catalyst in acid base catalysator, and it is acid site that catalysis derives from the acid sites with catalytic activity existing on solid surface.Their majorities are oxide compound or the mixed oxide of non-transition element, and its catalytic performance is different from the oxide catalyst containing transition element.This class catalyzer is widely used in the catalyzed reaction of ionic mechanism, and kind is a lot.
More preferably, the present invention selects profit to carry a type solid acid catalyst, by liquid acid appendix on solid carrier and forms, as a sulfuric acid profit year solid acid catalyst.
In a specific embodiment of the present invention, described solid acid is sieve and silica-sesquioxide, zirconium white, titanium oxide, heteropolyacid and corresponding solid super-strong acid.
As preferably, the mass ratio of described solid acid and biomass is 0.1: 1～10: 1, and optimum is 1: 3～1: 1.
In an embodiment, the present invention detects the content of levoglucosenone in product by marker method by gas-chromatography.Marker method is in analyzing working sample during certain component concentration, add a kind of internal standard substance matter with school who and eliminate impact analytical results being produced for the fluctuation of operational condition, to improve the accuracy of analytical results.Marker method is a kind of important technology in chromatogram ration analysis.While using marker method, in sample, add a certain amount of reference material, it can by chromatogram lean on separation, the not interference of other component peaks in test sample again, as long as measure peak area and the relative response(value) of internal standard substance and component to be measured, can obtain the percentage composition of component to be measured in sample.Take equal tetramethyl-benzene as internal standard substance, by peak area, determine levoglucosenone content, result demonstration, the method for the invention levoglucosenone productive rate can be brought up to more than 15%.
Major advantage of the present invention is as follows:
1) technique is simple, easy to operate;
2) the present invention's biomass material used and acid catalyst is common is easy to get, with low cost;
3) the present invention makees catalyzer with solid acid, can reclaim and reuse, and has avoided biomass pre-treatment step simultaneously, has also reduced sour corrodibility and contaminative;
4) product yield that the present invention obtains is high, compares with the productive rate of prior art 6% left and right, and the productive rate of levoglucosenone of the present invention can significantly be brought up to more than 15%;
5) the present invention has reduced the temperature of pyrolytic reaction, makes processing condition stability and safety more.
Accompanying drawing explanation
Fig. 1 is levoglucosenone gas phase collection of illustrative plates.
Embodiment
The invention discloses a kind of method of levoglucosenone of being prepared by acid catalysis pyrolysis by biomass, those skilled in the art can use for reference content herein, suitably improve processing parameter and realize.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are all deemed to be included in the present invention.Method of the present invention and application are described by preferred embodiment, related personnel obviously can change methods and applications as herein described or suitably change and combination within not departing from content of the present invention, spirit and scope, realizes and apply the technology of the present invention.
In order to make those skilled in the art understand better technical scheme of the present invention, below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1:
It is that the sulfuric acid of 0.1M floods that 55g bagasse is put into 550ml concentration, filters drying and processing.The vitriolated bagasse of handling is carried out to pyrolysis at 300 ℃, collect liquid, contain the bio oil of levoglucosenone.
Embodiment 2
It is that the sulfuric acid of 0.8M and the mixture of boric acid flood that 10g bagasse is put into 100ml concentration, filters drying and processing.The vitriolated bagasse of handling is carried out to pyrolysis at 260 ℃, collect liquid, contain the bio oil of levoglucosenone.
Embodiment 3
It is that the aqueous solution of 1M floods that 10g sial nano solid acid is put into 100ml sulfuric acid concentration, filtering drying, is downloaded to barium white on solid acid, after 2g solid acid is mixed with 3g bagasse, at 330 ℃, carries out pyrolysis, collect liquid, contain the bio oil of levoglucosenone.
Embodiment 4
After 10g sial nano solid acid is mixed with 10g bagasse, at 330 ℃, carry out pyrolysis, collect liquid, contain the bio oil of levoglucosenone.
Embodiment 5
After 10g titanium oxide solid acid is mixed with 20g Microcrystalline Cellulose, at 330 ℃, carry out pyrolysis, collect liquid, contain the bio oil of levoglucosenone.
Embodiment 6
It is that the aqueous solution of 1M floods that 10g titanium oxide solid acid is put into 100ml sulfuric acid concentration, filtering drying, barium white is downloaded on solid acid, 600 ℃ of calcinings, after being mixed with 20g Microcrystalline Cellulose, solid acid after calcining carries out pyrolysis at 330 ℃, collect liquid, contain the bio oil of levoglucosenone.
Embodiment 7
5g Microcrystalline Cellulose is put into sulfuric acid that 50ml concentration is 0.5M and the mixture of 0.1M zinc chloride floods, filter.The vitriolated Microcrystalline Cellulose of handling is carried out to pyrolysis at 330 ℃, collect liquid, contain the bio oil of levoglucosenone.
Embodiment 8
It is that the sulfuric acid of 0.5M and the mixture of hydrochloric acid flood that 10g poplar is put into 100ml concentration, filters, and dries.The vitriolated poplar of handling is carried out to pyrolysis at 320 ℃, collect liquid, contain the bio oil of levoglucosenone.
Embodiment 9
It is that the sulfuric acid of 0.5M floods that 20g bamboo is put into 200ml concentration, filters drying and processing.The vitriolated bamboo of handling is carried out to pyrolysis at 300 ℃, collect liquid, contain the bio oil of levoglucosenone.
Embodiment 10: the mensuration of levoglucosenone content
To in embodiment 1-9, through the resulting product of purifying, pass through gas-chromatography, wherein, the color atlas of the levoglucosenone that embodiment 2 obtains from bagasse is shown in Fig. 1, according to marker method, take equal tetramethyl-benzene as internal standard substance, by peak area, determines content.The results are shown in Table 1.
Method levoglucosenone assay described in table 1, embodiment 1-9
Embodiment 11: the purification of product levoglucosenone
The bio oil that embodiment 1-9 is obtained is neutralized to pH=7 with 1M sodium carbonate solution, then use dichloromethane extraction, then 100 ℃ of normal pressures revolve and boil off organic solvent and lower boiling component, and boiling point 70-80 ℃ is controlled in last underpressure distillation, obtains product levoglucosenone.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (2)
1. a method of preparing levoglucosenone, is characterized in that, comprises the following steps:
1) biomass are contacted with acid, described acid is the mixture of solid acid, sulfuric acid or sulfuric acid and other liquid acid; Described solid acid is sieve and silica-sesquioxide; Described other liquid acid are hydrochloric acid, iron(ic) chloride, zinc chloride or boric acid; The ratio of described biomass and aq acid soln is 1g:10ml, and acid concentration is 0.001M～3M; The mass ratio of described solid acid and biomass is 1:3～1:1;
2) in temperature, be at 200～380 ℃, to carry out pyrolysis, collect liquid, isolate levoglucosenone.
2. method according to claim 1, is characterized in that, contact for flood biomass oven dry or biomass being mixed with solid acid in aq acid soln described in step 1).
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| CN201110134871.9A CN102250158B (en) | 2011-05-23 | 2011-05-23 | Method for preparing levoglucosenone |
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| CN102250158B true CN102250158B (en) | 2014-03-26 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102660311B (en) * | 2012-05-10 | 2015-01-07 | 华北电力大学 | Method for preparing liquid fuel by performing catalytic pyrolysis on biomass by using magnetic titanium-based catalyst |
| CN102660312B (en) * | 2012-05-10 | 2014-06-25 | 华北电力大学 | Method for preparing liquid fuel by performing catalytic pyrolysis on biomass by using magnetic zirconium-based catalyst |
| CN103421529B (en) * | 2012-05-16 | 2015-01-21 | 中国科学院化学研究所 | Biomass catalytic pyrolysis method and ceramic solid acid catalyst |
| CN102816187B (en) * | 2012-08-28 | 2015-04-15 | 华北电力大学 | Levoglucosenone preparation method |
| CN106622203A (en) * | 2017-01-09 | 2017-05-10 | 东南大学 | Method for preparing levorodextrone based on pyrolytic carbon-catalyzed cellulose |
| CN108822877A (en) * | 2018-05-29 | 2018-11-16 | 柳州东侯生物能源科技有限公司 | The method of domestic waste cracking preparation combustion gas |
| CN109692690B (en) * | 2018-12-24 | 2020-08-25 | 华中科技大学 | Catalyst for producing levoglucosenone and preparation method thereof |
| CN112553004B (en) * | 2020-12-14 | 2022-06-21 | 湖北中烟工业有限责任公司 | Tobacco flavor and preparation method thereof |
| CN114853777B (en) * | 2022-06-14 | 2024-03-01 | 华北电力大学 | Catalytic pyrolysis method for preparing LGO |
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| CN101735282A (en) * | 2009-11-20 | 2010-06-16 | 中国科学技术大学 | Method for preparing laevoglucose ketone and special reaction equipment thereof |
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| JPH11152249A (en) * | 1997-11-21 | 1999-06-08 | Mitsubishi Chemical Corp | Production of unsaturated carboxylic acid ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101735282A (en) * | 2009-11-20 | 2010-06-16 | 中国科学技术大学 | Method for preparing laevoglucose ketone and special reaction equipment thereof |
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