CN109499612A - A kind of polyacid catalyst and its preparation method and application - Google Patents
A kind of polyacid catalyst and its preparation method and application Download PDFInfo
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- CN109499612A CN109499612A CN201811544825.4A CN201811544825A CN109499612A CN 109499612 A CN109499612 A CN 109499612A CN 201811544825 A CN201811544825 A CN 201811544825A CN 109499612 A CN109499612 A CN 109499612A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
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Abstract
The invention discloses a kind of polyacid catalyst containing lewis acid and bronsted acid, the purposes of glucose is prepared for hydrolyzing shinyleaf yellowhorn shell, and catalyst is the polyacid Ag for containing titanium, silverxH5‑ xPW11TiO40(0 x≤5 <), hydrolysis process shinyleaf yellowhorn shell can have the characteristics that synthesis is simple, catalytic activity is high, reusable in case of glucose, catalyst, and whole process is environmentally protective.
Description
Technical field
The present invention relates to catalyst preparation and applied technical field, more particularly to a kind of polyacid catalyst and its
The application of preparation method and polyacid catalyst in terms of shinyleaf yellowhorn shell base cellulose hydrolysis.
Background technique
Biomass energy is the important energy source that the mankind depend on for existence always, is only second to coal, oil and natural gas.Due to petrochemical industry
Resource it is increasingly depleted and a large amount of use and caused by problem of environmental pollution so that countries in the world are more and more sight
Concentrate on biomass energy using upper.It is estimated that mid-21st Century employ new technology production different kind organism matter substitution combustion
Material will account for 40% or more of global total energy consumption, become the major part of the following sustainable energy system.And with world wide
Interior oil crisis is got worse, and various countries accelerate to seek process route that is new, not preparing chemicals using petroleum as raw material, and
Formulate and implement the plan of corresponding exploitation biomass resource.Wherein, biomass material (such as starch, cellulose, sugar, vegetable are utilized
Rape oil or vegetable and animals oils etc.) bioenergy molecule is prepared by chemical method conversion replaces traditional fossil fuel, it is biomass
The basis that can be utilized and key.Therefore, designing chemical new process novel, efficient, environmental-friendly, under temperate condition is biomass
Hot spot and forward position of the key and environmental resource that can be utilized using area research.
Shiny-leaved yellowhorn is a kind of distinctive ecology of northern China, energy tree species, is classified as Eleventh Five-Year Plan in by country within 2006
Long-term four kinds one of the tree species given priority to.The economic value of shiny-leaved yellowhorn is very high, is known as " 1 year kind, the iron that a century is received by the masses
Bar crops ", cellulose rich in shinyleaf yellowhorn shell can be converted into monosaccharide or levulinic acidification under acidic conditions
Product.But the main component of shinyleaf yellowhorn shell base cellulose is made of β-Isosorbide-5-Nitrae-glycosidic bond, solubility in water is very low, difficult
With degradation.Therefore the structure of effective depolymerizing cellulose, makes it be converted into the useful hardware and software platform such as glucose or levulic acid
Object is closed, is the important prerequisite and key of Resources and utilization.Traditional minerals acid, such as sulphuric acid hydrolysis fibrin reaction obtain
To glucose, the usually reaction of high temperature, high acid concentration, and perishable instrument, higher energy is consumed, is also had serious
Problem of environmental pollution.
Polyoxometallate (POMs) is also referred to as polyacid, has strong bronsted acid, is a kind of nontoxic solid
Catalyst.Until now, structure with Keggin is relatively common, and to vacant polyoxometallate H5PW11TiO40The comparison of research
Vacant polyoxometallate H few, that silver replaces5PW11TiO40That studies is less.
Therefore, how a kind of green non-pollution, the polyacid catalyst that at low cost, hydrolysis property is excellent and its preparation side are provided
The problem of method and application are those skilled in the art's urgent need to resolve.
Summary of the invention
In view of this, the present invention provides the polyacid catalyst of a kind of high bronsted acid and lewis acidity appropriate
AgxH5-xPW11TiO40, the hydrolysis for shinyleaf yellowhorn shell prepares glucose.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of polyacid catalyst, the structural formula of the polyacid catalyst are AgxH5-xPW11TiO40, wherein x=1-5.
Preferably, in a kind of above-mentioned polyacid catalyst, the structural formula of the polyacid catalyst includes AgH4PW11TiO40、
Ag2H3PW11TiO40、Ag3H2PW11TiO40、Ag4HPW11TiO40And Ag5PW11TiO40。
The present invention also provides a kind of preparation methods of polyacid catalyst, comprising the following steps:
(1) by vacant polyacid compound H5PW11TiO40It is dissolved by heating with distilled water；
(2) AgNO is added dropwise thereto again3Solution is stirred to react to obtain mixed liquor；
(3) mixed liquor is aged, solid is precipitated, filter separation, washing precipitating, until the anion in solution is complete
Full removal；
(4) sediment is calcined, obtains the polyacid catalyst for preparing glucose.
Preferably, in a kind of above-mentioned preparation method of polyacid catalyst, vacant polyacid compound H5PW11TiO40With
AgNO3Molar ratio be 1:(1-5).
Preferably, in a kind of above-mentioned preparation method of polyacid catalyst, the quality that distilled water is added in step (1) is
H5PW11TiO405-10 times of quality.
Preferably, in a kind of above-mentioned preparation method of polyacid catalyst, heating that step (1) is 30-60 DEG C in temperature
It is carried out in environment, preferably 50-60 DEG C, if the excessively high catalytic activity that can destroy catalyst of temperature, too low to be unfavorable for filling for reactant
Tap touching, influences reaction process.
Preferably, in a kind of above-mentioned preparation method of polyacid catalyst, step is stirred to react 1-8h in (2).
Preferably, in a kind of above-mentioned preparation method of polyacid catalyst, digestion time is 2-4h in step (3), can be with
The precipitating of generation is adequately separated out, the collection processing of catalyst is more conducive to.
Preferably, in a kind of above-mentioned preparation method of polyacid catalyst, calcination condition is 150-300 DEG C in step (4)
2-4h is calcined, preferably 200 DEG C calcining 4h can make catalyst lose the crystallization water under this calcination condition, and structure is more stable,
It is more uniform.
The invention also discloses a kind of application of polyacid catalyst, the polyacid catalyst is for being catalyzed shinyleaf yellowhorn shell hydrolysis
Prepare glucose.
Preferably, above-mentioned polyacid catalyst glucose is prepared applied to hydrolysis shinyleaf yellowhorn shell to include the following steps:
(1) shinyleaf yellowhorn shell powder, catalyst and water are added in reaction kettle, are reacted in a heated condition；
(2) after reaction, reaction mixture is centrifuged, wherein lower sediment be unreacted cellulose and
Catalyst, product glucose are present in lower layer's aqueous phase solution；
(3) lower layer's aqueous phase solution is evaporated under reduced pressure at 40 DEG C, collects glucose after distilling out moisture.
Preferably, the mass ratio of shinyleaf yellowhorn shell powder, catalyst and water is 1:1-5:70 in step (1), in this ratio model
Conversion ratio and the glucose yield for enclosing shinyleaf yellowhorn shell are maximum.
Preferably, the reaction of step (1) carries out at being 130-170 DEG C in temperature, reaction time 5-12h.
It can be seen via above technical scheme that compared with prior art, the present disclosure provides a kind of polyacid catalyst
AgxH5-xPW11TiO40, reach following excellent technical effect:
1, silver disclosed by the invention replaces the polyacid solid catalyst H of titaniferous5PW11TiO40, than Keggin-type
H3PW12O40There is the proton of more high quality, shinyleaf yellowhorn shell can be promoted to be hydrolyzed to glucose, while introducing Lewis Acid metal
Ti4+And Ag+, the acidity of polyacid itself can be reinforced, further promoting shinyleaf yellowhorn shell hydrolysis is glucose；
2, it is disclosed by the invention be a kind of solid catalyst, can be used as heterogeneous catalysis recycling, green nothing
Pollution reduces economic cost；
3, polyoxometallate solid catalyst of the present invention can adjust catalyst by adjusting the content of silver
Activity, the polyacid solid catalyst of different substituted titaniferous is synthesized by design, and then obtain different bronsted acid and road
The catalyst of Lewis acid characteristic meets the needs of shinyleaf yellowhorn shell hydrolysis, adaptable.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The embodiment of the invention discloses the polyacid catalyst of a kind of high bronsted acid and lewis acidity appropriate
AgxH5-xPW11TiO40, the hydrolysis for shinyleaf yellowhorn shell prepares glucose.
The yield of present invention preparation polyacid catalyst and the catalytic effect of catalyst are carried out below by specific embodiment
Analytic explanation.
1:x (x=1-5) weighs vacant polyacid compound H respectively in molar ratio5PW11TiO40And AgNO3, omission
Polyacid compound H5PW11TiO40It is added in reactor, the distilled water that mass ratio is 1:5-10 is added, be heated to 30-60 DEG C, stirring
Dissolution；It is dropwisely added AgNO thereto again3Solution stirs 8 hours, and solution is aged 2-4 hours at room temperature after reaction, is precipitated
Solid filters separation, with distilling water washing and precipitating 2-3 times, until not having Ag in solution+, obtain sediment；The sediment is placed in
In Muffle furnace, in 150-300 DEG C calcining 2-4 hours, obtain the Ag of x=1-5xH5-xPW11TiO40Catalyst, and its yield is measured,
It the results are shown in Table 1:
Table 1
Shinyleaf yellowhorn shell powder, embodiment the 1-5 catalyst being prepared and water are added according to a certain percentage (1:x:70)
Enter into reaction kettle, set 130 DEG C~170 DEG C of reaction temperature, the reaction time is 5~12 hours, and shinyleaf yellowhorn shell is made to hydrolyze to obtain
Glucose；After reaction, it is centrifugated out catalyst and unreacted cellulose, repeats trans-utilization, product glucose is deposited
It is in water phase, measures the conversion ratio of shinyleaf yellowhorn shell and the yield of glucose, the results are shown in Table 2:
Table 2
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of polyacid catalyst, which is characterized in that the structural formula of the polyacid catalyst is AgxH5-xPW11TiO40, wherein x=
1-5。
2. a kind of polyacid catalyst according to claim 1, which is characterized in that the structural formula of the polyacid catalyst includes
AgH4PW11TiO40、Ag2H3PW11TiO40、Ag3H2PW11TiO40、Ag4HPW11TiO40And Ag5PW11TiO40。
3. a kind of preparation method of -2 described in any item polyacid catalyst according to claim 1, which is characterized in that including following
Step:
(1) by vacant polyacid compound H5PW11TiO40It is dissolved by heating at 30-60 DEG C with distilled water；
(2) AgNO is added dropwise thereto again3Solution is stirred to react to obtain mixed liquor；
(3) mixed liquor is aged, solid is precipitated, filter separation, washing precipitating；
(4) sediment is calcined, obtains the polyacid catalyst for preparing glucose.
4. a kind of preparation method of polyacid catalyst according to claim 3, which is characterized in that vacant polyacid compound
H5PW11TiO40With AgNO3Molar ratio be 1:x.
5. a kind of preparation method of polyacid catalyst according to claim 3, which is characterized in that be added and steam in step (1)
The quality of distilled water is H5PW11TiO405-10 times of quality.
6. a kind of preparation method of polyacid catalyst according to claim 3, which is characterized in that calcine item in step (4)
Part is 150-300 DEG C of calcining 2-4h.
7. a kind of application of -2 described in any item polyacid catalyst according to claim 1, which is characterized in that the polyacid catalysis
Agent prepares glucose for being catalyzed shinyleaf yellowhorn shell hydrolysis.
8. a kind of application of polyacid catalyst according to claim 7, which comprises the steps of:
(1) shinyleaf yellowhorn shell powder, catalyst and water are added in reaction kettle, are reacted in a heated condition；
(2) after reaction, reaction mixture is centrifuged, wherein lower sediment is unreacted cellulose and catalysis
Agent, product glucose are present in lower layer's aqueous phase solution；
(3) lower layer's aqueous phase solution is evaporated under reduced pressure, collects glucose after distilling out moisture.
9. a kind of application of polyacid catalyst according to claim 8, which is characterized in that shinyleaf yellowhorn shell powder in step (1)
The mass ratio at end, catalyst and water is 1:1-5:70.
10. a kind of application of polyacid catalyst according to claim 8, which is characterized in that the reaction of step (1) is in temperature
It is to be carried out at 130-170 DEG C, reaction time 5-12h.
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| CN201811544825.4A CN109499612B (en) | 2018-12-17 | 2018-12-17 | Polyacid catalyst and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569939A (en) * | 2020-06-04 | 2020-08-25 | 吉林建筑大学 | Pickering type polyacid catalyst, preparation method thereof and method for catalyzing cellulose hydrolysis |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106902877A (en) * | 2016-11-04 | 2017-06-30 | 北华大学 | A kind of many acid catalysts and preparation method thereof and application method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106902877A (en) * | 2016-11-04 | 2017-06-30 | 北华大学 | A kind of many acid catalysts and preparation method thereof and application method |
Non-Patent Citations (4)
| Title |
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| CHUNYAN FAN，ET AL.: "Conversion of fructose and glucose into 5-hydroxymethylfurfural catalyzed by a solid heteropolyacid salt", 《BIOMASS AND BIOENERGY》 * |
| KEN-ICHI SHIMIZU,ET AL.: "Effects of Bronsted and Lewis acidities on activity and selectivity of heteropolyacid-based catalysts for hydrolysis of cellobiose and cellulose", 《GREEN CHEMISTRY》 * |
| TAO, M. ET AL.: "Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts Applied in Esterification and Transesterification Reactions", 《SCIENTIFIC REPORTS》 * |
| XUEYAN ZHANG,ET AL.: "Catalyzing Cascade Production of Methyl Levulinate from Polysaccharides Using Heteropolyacids HnPW11MO39 with Brønsted/Lewis Acidic Sites", 《SUSTAINABLE CHEM. ENG.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569939A (en) * | 2020-06-04 | 2020-08-25 | 吉林建筑大学 | Pickering type polyacid catalyst, preparation method thereof and method for catalyzing cellulose hydrolysis |
| CN111569939B (en) * | 2020-06-04 | 2022-11-15 | 吉林建筑大学 | Pickering type polyacid catalyst, preparation method thereof and method for catalyzing cellulose hydrolysis |
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