CN103626808B - A kind of green method preparing the levoglucosenone of high added value - Google Patents
A kind of green method preparing the levoglucosenone of high added value Download PDFInfo
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- CN103626808B CN103626808B CN201210296301.4A CN201210296301A CN103626808B CN 103626808 B CN103626808 B CN 103626808B CN 201210296301 A CN201210296301 A CN 201210296301A CN 103626808 B CN103626808 B CN 103626808B
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- levoglucosenone
- phosphoric acid
- acid salt
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Abstract
What the present invention relates to is a kind of green method preparing the levoglucosenone of high added value, comprise following processing step: 1) Mierocrystalline cellulose or wood fiber biomass are contacted with phosphoric acid salt, described phosphoric acid salt can be single phosphoric acid salt or contain phosphatic mixture, and the mass ratio of phosphoric acid salt and wood fiber biomass mechanically mixing is 0.01:1 ~ 100:1; 2) under anaerobic, carry out pyrolysis at 200 ~ 700 DEG C, the time of pyrolysis is greater than 0.0001s, and product collects liquid after condensation, then isolates levoglucosenone; Advantage: lignocellulose raw material is common to be easy to get, the cheap and good stability of phosphoric acid salt used, pyrolysis temperature is low, and the selectivity of levoglucosenone is very high; By using phosphoric acid salt that is cheap and that recycle, effectively reducing production cost and reducing corrodibility and the contaminative of acid, is prepare the green economy of levoglucosenone and effective means.
Description
Technical field
What the present invention relates to is a kind of green method preparing the levoglucosenone of high added value.Belong to levoglucosenone preparing technical field.
Background technology
The bio oil that biomass pyrolytic obtains has very high utility value, it can not only as the alternate resources of fossil energy, also by the refining chemical obtaining many high values, as furfural (FF), levoglucosenone (LGO), Levoglucosan (LG), 1,4:3,6-two dehydration-D-Glucopyranose (DGP), glycollic aldehyde (HAA), 5 hydroxymethyl furfural (HMF) etc.But because the various composition of bio oil composition that non-catalytic pyrolysis is obtained is complicated, make extraction one-component carry out scale operation very difficult.
Levoglucosenone (levoglucosenone, 1,6-dewater-3,4-dideoxy-β-D-pyrans thin malt sugar-2-ketone) is the important pyrolysis product of the one of Mierocrystalline cellulose under acid catalyst effect, and its structure was determined in 1973 years.Levoglucosenone (LGO)
being that one has optically active chiral synthesize substrate, is effective Michael acceptor, the diene nucleophilic thing of Diels-Alder reaction and the dipolarophile body of Dipolar Cycloaddition.LGO application is very extensive, can be used for making various chiral adjuvant, many kinds of substance such as synthesis tetraodotoxin, RAS gene inhibitor etc.The many organic natural product intermediate synthesized by LGO also has its using value in field of biological pharmacy, new research finds that LGO may be used for synthesizing multiple Therapeutic cancer, immunological disease and cardiopathic pharmaceutical intermediate, may be used for synthetic antibiotic, immunosuppressor, pheromone and fragrance chemical (such as Whiskey lactone).LGO from being found apart from modern existing decades, but due to its productive rate not high, purifying is also very difficult, does not all produce on a large scale till now.This makes the price of LGO very high, and application aspect is subject to great restriction.
Wood fiber biomass pyrolysis especially fast pyrogenation can obtain the chemical of liquid fuel and high added value, is considered to utilize one of the most effective path for transformation of biomass energy.Catalyse pyrolysis can realize biomass and realize the chemical that orthoselection changes into high added value, thus improves the productive rate of one or more target products.A large amount of catalyzer generates levoglucosenone to Mierocrystalline cellulose or wood fiber biomass pyrolysis and all has certain katalysis, as H
3pO
4, H
2sO
4, SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2, ZnCl
2deng.Traditional method preparing levoglucosenone uses phosphate impregnation Mierocrystalline cellulose, and then fast pyrogenation on pyrolysis installation.But the phosphoric acid that this method for transformation uses has corrodibility and contaminative.Therefore, find a kind of catalyzer cheap, selectivity is good, the stable and method that can recycle to be to prepare levoglucosenone.
Summary of the invention
What the present invention proposed is a kind of green method preparing the levoglucosenone of high added value, overcomes the shortcomings such as the corrodibility of technique in the past, contaminative, levoglucosenone yield are low.
Technical solution of the present invention is realized by following steps:
1) Mierocrystalline cellulose or wood fiber biomass are contacted with phosphoric acid salt, described phosphoric acid salt can be single phosphoric acid salt or contain phosphatic mixture, and the mass ratio of its phosphoric acid salt and wood fiber biomass is 0.01:1 ~ 100:1;
2) under anaerobic, carry out pyrolysis at 200 ~ 700 DEG C, in the time pyrolysis through being greater than 0.0001s, product collects liquid after condensation, then isolates levoglucosenone.
The present invention has the following advantages:
1, the simple and environmental protection of technique, easy to operate;
2, the phosphoric acid salt that the present invention is used is solid catalyst, and catalyzer is cheap, have good stability, and can recycle, and also reduces corrosion and the pollution of acid;
3, phosphoric acid salt used is as catalyzer, and levoglucosenone selectivity is good, and levoglucosenone yield is high, the easy separating-purifying of product.
Accompanying drawing explanation
The total ion current figure of the bio oil obtained after the pyrolysis of accompanying drawing 1 Mierocrystalline cellulose.
Embodiment
The green method of levoglucosenone, comprises following processing step:
1) Mierocrystalline cellulose or wood fiber biomass are contacted with phosphoric acid salt, described phosphoric acid salt is single phosphoric acid salt or contains phosphatic mixture;
2) under anaerobic, carry out pyrolysis at 200 ~ 700 DEG C, the time of pyrolysis is greater than 0.0001s, and product collects liquid after condensation, then isolates levoglucosenone.
Described Mierocrystalline cellulose or wood fiber biomass contact with phosphoric acid salt is flooded in containing phosphatic solution by wood fiber biomass to dry (moisture content is less than 20wt.%) or by wood fiber biomass with containing phosphatic material mechanically mixing, the mass ratio of phosphoric acid salt and wood fiber biomass mechanically mixing is 0.01:1 ~ 100:1.
Described Mierocrystalline cellulose comprises Microcrystalline Cellulose, alpha-cellulose, absorbent cotton, and described wood fiber biomass raw material, comprises agricultural crop straw, timber, agriculture and forestry organic waste material.
Described phosphoric acid salt is the phosphate mixt of a kind of in trimagnesium phosphate, cupric phosphate, zinc phosphate, vanadium phosphorus oxide, tertiary iron phosphate or more than two kinds.
Described phosphoric acid salt is the mixture of phosphate hydrate of trimagnesium phosphate hydrate, cupric phosphate hydrate, Zinc Phosphate Hydrate, vanadium phosphorus oxide hydrate, tertiary iron phosphate hydrate a kind of or more than two kinds.
Described phosphoric acid salt is the phosphoric acid salt of loading type.
Under referring under described oxygen free condition that reaction system maintains vacuum or anaerobic shielding gas environment.
N under described atmosphere
2, Ar, He, H
2, CO
2in the mixed gas of one or two or more kinds.
Described vacuum refers to that the pressure in reaction system is less than 1 atmospheric condition.
Pyrolysis Experiment in embodiment described below is the internal diameter in dress with stove is that the crystal reaction tube of 40mm carries out, and reacts between the flat-temperature zone in stove and carries out.
Embodiment 1
By after 5g Microcrystalline Cellulose and 5g zinc phosphate mechanically mixing (mass ratio is 0.01:1) under anaerobic, carry out pyrolysis, pyrolysis time 2h after 200 DEG C of mixing, product collects liquid after condensation, namely the bio oil containing levoglucosenone, then isolate levoglucosenone.
Embodiment 2
By after 5g Microcrystalline Cellulose and 5g zinc phosphate mechanically mixing (mass ratio is 50:1) under anaerobic, carry out pyrolysis after 450 DEG C of mixing, product collects liquid after condensation, the bio oil namely containing levoglucosenone, then isolates levoglucosenone.
Embodiment 3
By after 10g Microcrystalline Cellulose and 5g zinc phosphate mechanically mixing (mass ratio is 100:1) under anaerobic, carry out pyrolysis, pyrolysis time 2h after 700 DEG C of mixing, product collects liquid after condensation, namely the bio oil containing levoglucosenone, then isolate levoglucosenone.
Embodiment 4
By after 5g Microcrystalline Cellulose or 5g cedar sawdust and 5g tertiary iron phosphate hydrate mechanically mixing under anaerobic, carry out pyrolysis after 350 DEG C or 450 DEG C of mixing, collect liquid, namely containing the bio oil of levoglucosenone, its GC-MS is shown in Fig. 1.Calculated by integral area, levoglucosenone in bio oil component content up to 65%.
Embodiment 5
After 450 DEG C of mixing, carry out vacuum (pressure in reaction system is less than 1 atmospheric condition) pyrolysis by after 5g cedar sawdust and 5g tertiary iron phosphate hydrate mechanically mixing, collect liquid, the bio oil namely containing levoglucosenone.
Embodiment 6
After 5g Mierocrystalline cellulose and 5g tertiary iron phosphate hydrate mechanically mixing, at 1atmN
2the lower 450 DEG C of pyrolysis of atmosphere collect liquid, the bio oil namely containing levoglucosenone.
Embodiment 7
After 5g Mierocrystalline cellulose and 5g tertiary iron phosphate hydrate mechanically mixing, under 1atmAr atmosphere, 450 DEG C of pyrolysis collect liquid, the bio oil namely containing levoglucosenone.
Embodiment 8
After 5g Mierocrystalline cellulose and 5g tertiary iron phosphate hydrate mechanically mixing, at 1atmCO
2the lower 450 DEG C of pyrolysis of atmosphere collect liquid, the bio oil namely containing levoglucosenone.
Embodiment 9
5g Mierocrystalline cellulose 200g is contained the aqueous impregnation of tertiary iron phosphate, then 60 DEG C of oven dry of spending the night under vacuum, at 1atmN
2the lower 450 DEG C of pyrolysis of atmosphere collect liquid, the bio oil namely containing levoglucosenone.
Embodiment 10
After mixing at 450 DEG C after 5g Mierocrystalline cellulose and 5g tertiary iron phosphate hydrate mechanically mixing, at 1atmH
2the lower 450 DEG C of pyrolysis of atmosphere collect liquid, the bio oil namely containing levoglucosenone.
Claims (1)
1. the green method for the preparation of levoglucosenone, it is characterized in that by after 5g Microcrystalline Cellulose or 5g cedar sawdust and 5g tertiary iron phosphate hydrate mechanically mixing under anaerobic, carry out pyrolysis after 350 DEG C or 450 DEG C of mixing, collect liquid, namely containing the bio oil of levoglucosenone.
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| CN103626808B true CN103626808B (en) | 2016-03-23 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105523783B (en) * | 2016-01-22 | 2019-11-22 | 南京林业大学 | A kind of method of stalk production high valuable chemicals coproduction slow-release fertilizer |
| CN106977557B (en) * | 2017-04-27 | 2019-10-29 | 河南城建学院 | A kind of preparation method of levoglucosenone |
| CN107603649B (en) * | 2017-10-25 | 2019-11-22 | 华中科技大学 | It is a kind of richness ketone bio oil and rich magnesium active carbon preparation method |
| CN112646596A (en) * | 2019-10-11 | 2021-04-13 | 中国科学院大连化学物理研究所 | Biomass pretreatment method for improving selectivity of high-value chemicals in pyrolysis oil |
| CN114853777B (en) * | 2022-06-14 | 2024-03-01 | 华北电力大学 | Catalytic pyrolysis method for preparing LGO |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (5)
| Title |
|---|
| Application of catalysts for obtaining 1,6-anhydrosaccharides from cellulose and wood by fast pyrolysis;G. Dobele等;《J. Anal. Appl. Pyrolysis》;20050317;第74卷;401-405 * |
| Mechanocatalysis for biomass-derived chemicals and fuels;Sandra M. Hick等;《Green Chem.》;20100125;第12卷;468-474 * |
| Phosphorus catalysis in the pyrolysis behaviour of biomass;Daniel J. Nowakowski等;《J. Anal. Appl. Pyrolysis》;20080819;第83卷;197-204 * |
| 木质纤维类生物质定向热解行为研究;刘军利;《中国博士学位论文》;20120415;1-181 * |
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