CN105080608B - A kind of application of more acid catalysts in cellulose hydrolysis - Google Patents
A kind of application of more acid catalysts in cellulose hydrolysis Download PDFInfo
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- CN105080608B CN105080608B CN201410189041.XA CN201410189041A CN105080608B CN 105080608 B CN105080608 B CN 105080608B CN 201410189041 A CN201410189041 A CN 201410189041A CN 105080608 B CN105080608 B CN 105080608B
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- acid catalysts
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- cellulose
- cellulose hydrolysis
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Abstract
The present invention relates to a kind of more acid catalysts of catalytic cellulose to glucose, are the polyacid compounds with Dawson structures；Glucose is prepared with this catalyst.Catalyst has high catalytic activity, repeatability and extensive adaptability to raw materials.Whole preparation process produces without waste water, green.
Description
Technical field
The present invention is catalyst preparation and applied technical field, and in particular to a kind of new nano-solid heteropoly acid catalysis
Agent.Application the invention further relates to this nanocatalyst in terms of cellulose hydrolysis simultaneously.
Technical background
Cellulose is widely existed in nature, is a kind of reproducible biomass energy species.Cellulosic molecule is
Formed by many individual glucose molecules by β-Isosorbide-5-Nitrae glycoside link, it is insoluble in water and in most organic solvents and cause difficulty
Degraded and difficult plasticity.Therefore, the premise that cellulose effectively utilizes is to reduce its degree of polymerization.The method used in the world at present is main
There are physical method (thermal degradation, radiation degradation and mechanical degradation), biological method (enzymatic degradation) and chemical method (oxidative degradation
And hydrolysis).Wherein chemical method includes oxidative degradation and hydrolysis, wherein can be reduced sugar by cellulose decomposition by hydrolysis,
It is the important step of cellulose resource exploitation and the premise utilized.But because the crystalline texture of cellulose causes cellulose
Hydrolysis is difficult, and crystallinity is higher, and hydrolysis is more difficult.Therefore how to be effectively that monose turns into current by cellulose hydrolysis
The key that constraints on fiber element utilizes.Traditional inorganic acid such as H2SO4Catalyzing cellulose hydrolysis reaction prepares glucose, usually uses
High concentrated acid, high temperature (170-240 DEG C), react for a long time so as to cause catabolite complexity, high energy consumption, equipment corrosion, technique
The problems such as complicated, a large amount of spent acid and environmental pollution, it has also become the technical bottleneck [3] of constraints on fiber element large-scale production.
Heteropoly acid (HPAs) has unique Acidity and higher than dense H2SO4More than hundred times of acid strength, as green acid catalysis
Agent, it is increasingly subject to the concern of people.Study at present it is more be structure with Keggin polyacid such as H3PW12O40Deng, and Wells-
Dawson structure heteropoly acids H6P2W18O62Study less.And H3PW12O40Compare, H6P2W18O62With more protons, in water
It is ionizable go out more protons come meet cellulose hydrolysis needs.
Can be during cellulose switchs to for glucose as catalyst by the use of the polyoxometallate of Dawson structures
Solve many technical problems：
1st, the polyacid of Dawson structures has high proton content, can meet the needs of cellulose hydrolysis.
2nd, more acid systems are solid acid catalysts.Polyoxometallate is urged in vegetable oil reaction system as out-phase reaction
Agent, it is easy to separate from reaction system, does not produce substantial amounts of pollution sewage, and it is reusable, reduce catalyst use cost.
3rd, polyacid solid catalyst reacts in " nanometer system ".The self assembly in water of polyacid solid catalyst is that nanometer is anti-
Device is answered, improves reactivity.
4th, the adjustability of polyoxometallate catalysis of solid catalyst activity.
By design synthesize different compositions, different-shape, different crystal water contents, different acid strengths more acid catalysts,
Cellulose hydrolysis needs can be met, it is practical.
The content of the invention
The present invention provides a kind of highAcid nanometer polyacid [C16H33(CH3)3N]nH6-n[P2W18O62]·6H2O
Catalyst, glucose is prepared for cellulose hydrolysis.To realize this purpose, it is practiced by following scheme.
A kind of solid nano catalyst has following method to be prepared：
In molar ratio 1：0-6 weighs polyacid compound H respectively6[P2W18O62]·6H2O and surfactant [C16H33
(CH3)3N]Br；Polyacid compound H6[P2W18O62]·6H2O is poured into reactor, and it is 1 to add mass ratio：5-10 times of distillation
Water, 50-60 DEG C is heated to, stirring and dissolving；Add surfactant thereto again, reaction solution ageing 5-10 hours, separate out solid
Thing, filtering, precipitated 2-3 times with distilled water flushing, until the pH value of eluate reaches 5-8, obtain sediment；The sediment is put
In horse kettle stove, 2-6 hours are sintered in 150-300 DEG C, that is, obtain a kind of more acid catalysts for preparing glucose.Its yield is
84%.
With a kind of more acid catalysts for preparing glucose provided by the invention, catalyzing cellulose hydrolysis prepares the side of glucose
Method is as follows：
By cellulose powder, catalyst and water according to a certain percentage (1:4.19:70) it is added in reactor, setting reaction
130 DEG C~170 DEG C of temperature, 5~10h of reaction time, makes cellulose hydrolysis obtain glucose.The dosage 0.04 of catalyst~
0.13mmol.After reaction terminates, catalyst and unreacted cellulose are centrifuged out, repeats to convert.Product glucose is in water
Xiang Zhong, 40 DEG C steam water, obtain product, and yield is~50%.
Brief description of the drawings
(1) Fig. 1 is that the infrared spectrum a) of solid catalyst is fresh；B) reclaim
(2) Fig. 2 is solid catalysis31P solid state nmrs
Embodiment
Embodiment 1
Mol ratio 1 is weighed respectively：2 polyacid compound H6[P2W18O62]·6H2O and surfactant [C16H33(CH3)3N]
Br；Polyacid compound H6[P2W18O62]·6H2O is poured into reactor, is added the distilled water that mass ratio is 10 times, is heated to 50
DEG C, stirring and dissolving；Add surfactant thereto again, reaction solution is aged 6 hours, is separated out solids, filtering, is rushed with distilled water
Wash precipitation 3 times, until the pH value of eluate reaches 7.3, obtain sediment；The sediment is placed in horse kettle stove, in 160 DEG C of burnings
Knot 2 hours, that is, obtain a kind of more acid catalysts for preparing glucose.Its yield is 84%.
The structure infrared spectrum (see Fig. 1) of solid catalyst,31PMASNMR (see Fig. 2) is determined.
Embodiment 2
By cellulose powder 0.1g, 0.09mmol [C16H33(CH3)3N]H5[P2W18O62]·6H2O catalyst is put into instead
Answer in kettle, add 7mL deionized water, heating stirring.Reaction temperature is 160 DEG C, reaction time 8h.It is cold after reaction terminates
But reactant mixture is put into centrifuge tube afterwards and be centrifuged, glucose is included in clear liquid, is responseless in precipitation
Cellulose and catalyst.The conversion ratio of cellulose is 64.0%, and the yield of glucose sugar is 49.6%.Catalyst after recovery it is red
Outside as shown in Fig. 1 b).
Claims (2)
1. a kind of more acid catalysts that glucose is prepared for catalyzing cellulose hydrolysis, the formula of the catalyst are：
[C16H33(CH3)3N]nH6-n[P2W18O62]·6H2O, wherein n ≠ 0,
Wherein, catalyst is prepared by following method：
In molar ratio 1：M weighs polyacid compound H respectively6[P2W18O62]·6H2O and surfactant [C16H33(CH3)3N] Br,
Wherein 0<m≤6；Polyacid compound H6[P2W18O62]·6H2O is poured into reactor, and it is 1 to add mass ratio：5-10 times of steaming
Distilled water, 50-60 DEG C is heated to, stirring and dissolving；Add the surfactant, reaction solution ageing 5-10 hours, analysis thereto again
Go out solids, filter, precipitated 2-3 times with distilled water flushing, until the pH value of eluate reaches 5-8, obtain sediment；This is sunk
Starch is placed in Muffle furnace, is sintered 2-6 hours in 150-300 DEG C, that is, is obtained a kind of more acid catalysts for preparing glucose.
2. more acid catalysts as claimed in claim 1, it is characterised in that described more acid catalysts are：
[C16H33(CH3)3N]H5[P2W18O62]·6H2O,
[C16H33(CH3)3N]2H4[P2W18O62]·6H2O,
[C16H33(CH3)3N]3H3[P2W18O62]·6H2O,
[C16H33(CH3)3N]4H2[P2W18O62]·6H2O,
[C16H33(CH3)3N]5H[P2W18O62]·6H2O。
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| CN201410189041.XA CN105080608B (en) | 2014-05-06 | 2014-05-06 | A kind of application of more acid catalysts in cellulose hydrolysis |
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| CN201410189041.XA CN105080608B (en) | 2014-05-06 | 2014-05-06 | A kind of application of more acid catalysts in cellulose hydrolysis |
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| CN105080608A CN105080608A (en) | 2015-11-25 |
| CN105080608B true CN105080608B (en) | 2018-02-23 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106902877B (en) * | 2016-11-04 | 2019-08-30 | 北华大学 | A kind of polyacid catalyst and preparation method thereof and application method |
| CN110201712B (en) * | 2019-05-10 | 2021-12-07 | 东北师范大学 | Ionic liquid type polyoxometallate catalyst and preparation method and application thereof |
| CN110028397A (en) * | 2019-05-15 | 2019-07-19 | 东北师范大学 | A kind of application of the polyacid catalyst of the structure containing Dawson in cellulose hydrothermal conversion |
| CN113004123B (en) * | 2021-03-18 | 2022-07-26 | 青岛科技大学 | Method for preparing phloroglucinol |
| CN113185394A (en) * | 2021-04-15 | 2021-07-30 | 华南农业大学 | Method for preparing levulinic acid by using Dowson configuration tungsten-phosphorus heteropoly acid for catalyzing and hydrolyzing cellulose |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549288A (en) * | 2009-05-14 | 2009-10-07 | 北京化工大学 | Novel Dawson polyacid intercalation hydrotalcite composite material and method of preparing the same |
| CN104086603A (en) * | 2014-07-08 | 2014-10-08 | 吉林化工学院 | Structure and preparation method of imidazole modified phosphotungstate compound |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549288A (en) * | 2009-05-14 | 2009-10-07 | 北京化工大学 | Novel Dawson polyacid intercalation hydrotalcite composite material and method of preparing the same |
| CN104086603A (en) * | 2014-07-08 | 2014-10-08 | 吉林化工学院 | Structure and preparation method of imidazole modified phosphotungstate compound |
Non-Patent Citations (2)
| Title |
|---|
| Dawson结构[(HOCH2CH2)2NH2]6·P2W18O62·6H2O的合成、表征、晶体结构;郭东杰等;《化学研究》;20030630;第14卷(第2期);第24-27页 * |
| 固体杂多酸催化剂设计与合成在纤维素水解反应中的应用;程明星;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20130531;B016-100 * |
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