CN104549200B - Solid acid catalyst and application thereof in catalytically converting glucose to prepare methyl levulinate - Google Patents
Solid acid catalyst and application thereof in catalytically converting glucose to prepare methyl levulinate Download PDFInfo
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- CN104549200B CN104549200B CN201510037982.6A CN201510037982A CN104549200B CN 104549200 B CN104549200 B CN 104549200B CN 201510037982 A CN201510037982 A CN 201510037982A CN 104549200 B CN104549200 B CN 104549200B
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- acid catalyst
- solid acid
- methyl ester
- glucose
- ester levulinate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention discloses a solid acid catalyst and an application thereof in catalytically converting glucose to prepare methyl levulinate. The carrier of the catalyst is sodium-based montmorillonite, the active ingredient of which is any one of In<3+>, Cr<3+>, Cu<2+>, Sn<4+> and Al<3+>. The loading capacity of the active ingredient is 5-40wt.%. The catalyst is prepared by using an ion exchange method, the preparation method is simple, and the solid acid catalyst is good in stability, environment-friendly, free of pollution and less in corrosion on equipment, and the catalyst for catalytically converting glucose to prepare methyl levulinate is good in catalytic activity, high in selectivity, easy to be separated and recovered from reactants, recyclable and good in cycling stability, and can be used for fully catalytically converting glucose. The highest yield of methyl levulinate can reach over 60%.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to one and prepare levulic acid for catalyzed conversion glucose
The solid acid catalyst of methyl ester.
Background technology
Along with increasingly reducing of fossil fuel resource and becoming increasingly conspicuous of ecological environment problem, develop renewable
, eco-friendly biomass resource substitute fossil energy have become as domestic and international research worker pay close attention to focus.
Can prepare many kind chemical products from biomass resource, wherein methyl ester levulinate is exactly a kind of critically important
Platform chemicals.
Methyl ester levulinate has another name called 4-oxopentanoic acid methyl ester, colourless liquid, is soluble in ethanol, methanol, ether, chloroform
Etc. most of organic solvents, density is 1.051, boiling point 193～195 DEG C.Methyl ester levulinate molecular formula contains
One ester group, a carbonyl and two α-H, thus there is the highest reactivity, it is possible to be hydrolyzed, addition,
Reduce, replace, the reaction such as condensation, can be used as spice, chemical products, medical raw material, plasticizer etc., it is also possible to
Additive as Fuel Petroleum, diesel fuel and bio-fuel.
Methyl ester levulinate, as the important chemical products of a class, is mainly esterified method, biomass by levulic acid
Directly alcoholysis method and furfuryl alcohol alcoholysis method are prepared from.Solid acid catalyst is considered as the catalyst of a kind of environmental protection
And be widely used in organic chemical reactions, it have easily with reactants separate, process equipment simply, corrosivity
Little, environmental pollution is little and the advantage such as reusable.But, at present about utilizing solid acid catalyst to be catalyzed
Biomass alcoholysis is prepared in the report of levulinate, and the yield of levulinate all ratios are relatively low.Therefore, have very much
Necessity seeks a kind of more efficient, stable and environmentally friendly solid acid catalyst.
Summary of the invention
The technical problem to be solved is to solve to lack present in methyl ester levulinate technology existing preparation
Point is with not enough, and proposing a kind of catalyzed conversion glucose that can be used for prepares the solid acid catalyst of methyl ester levulinate, should
Method for preparing catalyst is simple, be catalyzed activity height, selectivity height, good stability, be easily isolated recovery, to environment
Friendly pollution-free.
Solve above-mentioned technical problem and be the technical scheme is that the carrier of this catalyst is sodium-based montmorillonite, live
Property component is In3+、Cr3+、Cu2+、Sn4+、Al3+In any one, the load capacity of active component be 5wt.%～
40wt.%.
The load capacity of above-mentioned active component is preferably 20wt.%～30wt.%, the preferred Sn of described active component4+
Or Al3+。
Solid acid catalyst of the present invention uses ion exchange to be prepared from, method particularly includes: according to active component
Load capacity is 5wt.%～40wt.%, the soluble-salt of active component is added in deionized water, ultrasonic agitation 30～
60 minutes, add sodium-based montmorillonite, stir 12 hours at 50～70 DEG C, stand 10～12 hours, sucking filtration,
Washing, 100～120 DEG C are dried overnight, and grind, obtain solid acid catalyst；Described active component solvable
Property salt is In3+、Cr3+、Cu2+、Sn4+、Al3+Soluble-salt in any one, such as villaumite etc..
Solid acid catalyst of the present invention prepares the purposes in methyl ester levulinate at catalyzed conversion glucose, its user
Method is: for 1:0.5～1:50～100, glucose is added reaction under high pressure in mass ratio with solid acid catalyst, methanol
Mix homogeneously in still, at 1.0～4.0MPa N2Under atmosphere, 150～250 DEG C are reacted 3～12 hours, are prepared as levulinic
Acid methyl ester.
Glucose is further preferably added height for 1:0.5:80 with solid acid catalyst, methanol by the present invention in mass ratio
Mix homogeneously in pressure reactor, at 2.0MPa N2Under atmosphere, it is warming up to 220 DEG C, constant temperature stirring reaction 6 hours, preparation
Become methyl ester levulinate.
The solid acid catalyst preparation method of the present invention is simple, good stability, environmentally friendly pollution-free, be used for urging
Change transforming glucose and prepare that the catalysis activity of methyl ester levulinate is good, selectivity is high, it is easy to separation and recovery, capable of circulation
Use and good cycling stability, and can catalyzed conversion glucose completely, the productivity of methyl ester levulinate is the highest can
Reach more than 60%.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in more detail, it should be noted that but the protection model of the present invention
Enclose and be not limited only to these embodiments.
Embodiment 1
Use ion exchange, be 20wt.% by aluminum ions load capacity, 1.2355g aluminum chloride is joined 50
In mL deionized water, ultrasonic agitation 30 minutes, add 1g sodium-based montmorillonite, stir 12 hours at 60 DEG C,
Stand 12 hours, sucking filtration, it is washed with deionized and exists to without chloride ion, 120 DEG C are dried overnight, and grind, system
Standby one-tenth solid acid catalyst.
Embodiment 2
Use ion exchange, be 5wt.% by aluminum ions load capacity, 0.2601g aluminum chloride is joined 50mL
In deionized water, ultrasonic agitation 30 minutes, add 1g sodium-based montmorillonite, stir 12 hours at 60 DEG C, quiet
Putting 12 hours, sucking filtration, be washed with deionized and exist to without chloride ion, 120 DEG C are dried overnight, and grind, preparation
Become solid acid catalyst.
Embodiment 3
Use ion exchange, be 10wt.% by aluminum ions load capacity, 0.5491g aluminum chloride is joined 50
In mL deionized water, ultrasonic agitation 30 minutes, add 1g sodium-based montmorillonite, stir 12 hours at 60 DEG C,
Stand 12 hours, sucking filtration, it is washed with deionized and exists to without chloride ion, 120 DEG C are dried overnight, and grind, system
Standby one-tenth solid acid catalyst.
Embodiment 4
Use ion exchange, be 30wt.% by aluminum ions load capacity, 2.1180g aluminum chloride is joined 50
In mL deionized water, ultrasonic agitation 30 minutes, add 1g sodium-based montmorillonite, stir 12 hours at 60 DEG C,
Stand 12 hours, sucking filtration, it is washed with deionized and exists to without chloride ion, 120 DEG C are dried overnight, and grind, system
Standby one-tenth solid acid catalyst.
Embodiment 5
Use ion exchange, be 40wt.% by aluminum ions load capacity, 3.2946g aluminum chloride is joined 50
In mL deionized water, ultrasonic agitation 30 minutes, add 1g sodium-based montmorillonite, stir 12 hours at 60 DEG C,
Stand 12 hours, sucking filtration, it is washed with deionized and exists to without chloride ion, 120 DEG C are dried overnight, and grind, system
Standby one-tenth solid acid catalyst.
Embodiment 6
Use ion exchange, be 20wt.% by the load capacity of indium ion, 0.4816g indium chloride is joined 50
In mL deionized water, ultrasonic agitation 30 minutes, add 1g sodium-based montmorillonite, stir 12 hours at 60 DEG C,
Stand 12 hours, sucking filtration, it is washed with deionized and exists to without chloride ion, 120 DEG C are dried overnight, and grind, system
Standby one-tenth solid acid catalyst.
Embodiment 7
Use ion exchange, be 20wt.% by the load capacity of chromium ion, 0.4077g Chlorizate chromium is joined 50
In mL deionized water, ultrasonic agitation 30 minutes, add 1g sodium-based montmorillonite, stir 12 hours at 60 DEG C,
Stand 12 hours, sucking filtration, it is washed with deionized and exists to without chloride ion, 120 DEG C are dried overnight, and grind, system
Standby one-tenth solid acid catalyst.
Embodiment 8
Use ion exchange, be 20wt.% by the load capacity of copper ion, 0.6707g copper chloride is joined 50
In mL deionized water, ultrasonic agitation 30 minutes, add 1g sodium-based montmorillonite, stir 12 hours at 60 DEG C,
Stand 12 hours, sucking filtration, it is washed with deionized and exists to without chloride ion, 120 DEG C are dried overnight, and grind, system
Standby one-tenth solid acid catalyst.
Embodiment 9
Use ion exchange, be 20wt.% by the load capacity of tin ion, 0.5486g stannic chloride is joined 50
In mL deionized water, ultrasonic agitation 30 minutes, add 1g sodium-based montmorillonite, stir 12 hours at 60 DEG C,
Stand 12 hours, sucking filtration, it is washed with deionized and exists to without chloride ion, 120 DEG C are dried overnight, and grind, system
Standby one-tenth solid acid catalyst.
Embodiment 10
The solid acid catalyst of embodiment 1～9 preparation prepares the use in methyl ester levulinate at catalyzed conversion glucose
On the way, its specifically used method is:
0.3g glucose, 0.15g solid acid catalyst, 24g methanol are added in autoclave, is passed through nitrogen
Air in displacement autoclave, in triplicate, is passed through the nitrogen of 2MPa, again at 500 revs/min under room temperature
Under stirring condition, being heated to 220 DEG C, isothermal reaction 6 hours, reaction terminates rear centrifugation catalyst, reaction
Liquid, with after the 0.22 organic membrane filtration of μm, with the productivity of gas Chromatographic Determination methyl ester levulinate, the results are shown in Table 1.
Table 1 solid acid catalyst of the present invention catalyzed conversion glucose prepares the productivity of methyl ester levulinate
| Catalyst | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Methyl ester levulinate productivity | 60.6% | 35.7% | 40.7% | 56.0% | 46.7% |
| Catalyst | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| Methyl ester levulinate productivity | 47.8% | 40.6% | 49.1% | 54.7% |
From table 1, solid acid catalyst of the present invention prepares urging of methyl ester levulinate for catalyzed conversion glucose
Change activity is good, selectivity is high.The solid acid catalyst of embodiment 1,6～9 is used for catalyzed conversion Fructus Vitis viniferae by inventor
Sugar reclaims through filtration drying, reuses after preparing methyl ester levulinate, reuses effect and is shown in Table 2.
What table 2 solid acid catalyst of the present invention catalyzed conversion glucose prepared methyl ester levulinate reuses effect
| Catalyst | Embodiment 1 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| 1st time | 60.6% | 47.8% | 40.6% | 49.1% | 54.7% |
| 2nd time | 53.2% | 40.4% | 36.1% | 26.7% | 47.5% |
| 3rd time | 43.1% | 31.9% | 30.5% | 19.6% | 41.5% |
From table 2, solid acid catalyst of the present invention can be recycled and good cycling stability.
The solid acid catalyst catalyzed conversion Portugal at different temperatures that embodiment 1 is prepared by inventor according to the method described above
Methyl ester levulinate prepared by grape sugar, and result of the test is shown in Table 3.
The solid acid catalyst of table 3 embodiment 1 catalyzed conversion glucose at different temperatures prepares the productivity of methyl ester levulinate
| Temperature (DEG C) | 160 | 180 | 200 | 220 | 240 |
| Methyl ester levulinate productivity | 30.9% | 40.7% | 48.7% | 60.6% | 41.8% |
From table 3, solid acid catalyst of the present invention catalyzed conversion glucose at 220 DEG C prepares levulic acid first
The effect of ester is best.
Claims (6)
1. solid acid catalyst prepares the purposes in methyl ester levulinate, described solid at catalyzed conversion glucose
The carrier of acid catalyst is sodium-based montmorillonite, and active component is In3+、Cr3+、Cu2+、Sn4+、Al3+In any one
Kind, the load capacity of active component is 5wt.%～40wt.%.
Solid acid catalyst the most according to claim 1 prepares methyl ester levulinate at catalyzed conversion glucose
In purposes, it is characterised in that: described active component is Sn4+Or Al3+。
Solid acid catalyst the most according to claim 1 prepares methyl ester levulinate at catalyzed conversion glucose
In purposes, it is characterised in that: the load capacity of described active component is 20wt.%～30wt.%.
4. prepare second according to the solid acid catalyst described in claims 1 to 3 any one at catalyzed conversion glucose
Purposes in acyl methyl propionate, it is characterised in that: described solid acid catalyst uses ion exchange to be prepared from.
Solid acid catalyst the most according to claim 1 prepares methyl ester levulinate at catalyzed conversion glucose
In purposes, it is characterised in that: by glucose and solid acid catalyst, methanol be in mass ratio 1:0.3～1:50～
100 add mix homogeneously in autoclave, 1.0～4.0MPaN2Under atmosphere, it is warming up to 150～250 DEG C, constant temperature
Stirring reaction 3～12 hours, is prepared as methyl ester levulinate.
Solid acid catalyst the most according to claim 1 prepares methyl ester levulinate at catalyzed conversion glucose
In purposes, it is characterised in that: by glucose and solid acid catalyst, methanol in mass ratio for 1:0.5:80 addition
Mix homogeneously in autoclave, at 2.0MPaN2Under atmosphere, it is warming up to 220 DEG C, constant temperature stirring reaction 6 hours, system
Standby one-tenth methyl ester levulinate.
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| CN108212207B (en) * | 2018-03-23 | 2021-01-01 | 陕西师范大学 | Solid acid catalyst for preparing methyl lactate by catalytic conversion of glucose and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3489795A (en) * | 1962-12-28 | 1970-01-13 | George Gal | Preparation of tertiary alkyl levulinates |
| CN102399144A (en) * | 2011-09-26 | 2012-04-04 | 华南理工大学 | Method for preparing methyl levulinate through clean conversion of biomass sugar and separating methyl levulinate |
| CN103408422A (en) * | 2013-07-25 | 2013-11-27 | 中科院广州化学有限公司 | High-yield levulinic acid ester preparation method under catalysis of solid acid |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891651B (en) * | 2009-05-19 | 2014-03-12 | 拜耳材料科技(中国)有限公司 | Catalyst used in preparation of N-substituted carbamate and preparation method and application thereof |
| CN103657689B (en) * | 2013-12-09 | 2016-05-04 | 陕西师范大学 | A kind of solid acid catalyst and preparation method thereof and at catalyzed conversion biomass-making for the application in lactic acid |
| CN104138753B (en) * | 2014-07-29 | 2016-08-17 | 华南理工大学 | A kind of tinbase montmorillonite catalyst is the application of furfural with preparation method and catalysis xylose thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3489795A (en) * | 1962-12-28 | 1970-01-13 | George Gal | Preparation of tertiary alkyl levulinates |
| CN102399144A (en) * | 2011-09-26 | 2012-04-04 | 华南理工大学 | Method for preparing methyl levulinate through clean conversion of biomass sugar and separating methyl levulinate |
| CN103408422A (en) * | 2013-07-25 | 2013-11-27 | 中科院广州化学有限公司 | High-yield levulinic acid ester preparation method under catalysis of solid acid |
Non-Patent Citations (1)
| Title |
|---|
| Conversion of triose sugars with alcohols to alkyl lactates catalyzed by Brønsted acid tin ion-exchanged montmorillonite;Jiacheng Wang等;《Applied Catalysis B: Environmental》;20110713;全文 * |
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