CN108950090A - A kind of method for hydrolysis of saccharide compound - Google Patents
A kind of method for hydrolysis of saccharide compound Download PDFInfo
- Publication number
- CN108950090A CN108950090A CN201810803458.9A CN201810803458A CN108950090A CN 108950090 A CN108950090 A CN 108950090A CN 201810803458 A CN201810803458 A CN 201810803458A CN 108950090 A CN108950090 A CN 108950090A
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- China
- Prior art keywords
- catalyst
- hydrolysis
- acid
- attapulgite
- saccharide compound
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Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K3/00—Invert sugar; Separation of glucose or fructose from invert sugar
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a kind of methods for being catalyzed polysaccharide hydrolysis, under solid catalyst effect, compound of polysaccharide is hydrolyzed to the process for generating monosaccharide, the solid catalyst is attapulgite, the thermalization at a certain temperature of natural attapulgite is handled, acidity of catalyst is regulated and controled at different temperatures through different Bronsted acids, it is catalyzed polysaccharide hydrolysis and generates monosaccharide, it is mild with reaction condition, all catalyst are cheap, the features such as environmental-friendly, simple process, catalyst is easily isolated and is reusable.
Description
Technical field
The invention belongs to technical field of chemical engineering catalysts, and in particular to a kind of catalyzed hydrolytic methods of saccharide compound.
Background technique
Carbohydrate is the important organic compound of one kind widely distributed in nature.In the sucrose of daily consumption, grain
Glucose in cellulose, blood of human body in starch, plant etc. belongs to carbohydrate.Carbohydrate during vital movement from emphatically
The effect wanted is that all life body sustains life the main source of energy needed for activity.In plant most important sugar be starch and
Cellulose, most important polysaccharide is glycogen in zooblast.Glucide is divided into monosaccharide, oligosaccharide (oligosaccharides), polysaccharide, glycoconjugate
Four kinds.Monosaccharide is the simplest one kind of carbohydrate kind structure, and monosaccharide molecule hydrophilic radical containing there are many is soluble easily in water, does not dissolve in second
Ether, acetone and other organic solvent, simple monosaccharide are usually polyhydroxy aldehyde or polyhydroxyketone containing 3-7 carbon atom, composition
Element is C, H, O glucose, fructose, galactolipin etc..Oligosaccharide (oligosaccharides), is polymerized, after hydrolysis by 2-10 monosaccharide molecule
Monosaccharide, including disaccharides, trisaccharide, tetrose etc. are produced, disaccharides is to be formed by two monosaccharide by glucosides key connection, after disaccharides hydrolysis
Generate two molecule monosaccharide.Common disaccharides has lactose, sucrose, maltose.Sucrose and maltose are to be hydrolyzed into monosaccharide energy supply.Three
The oligosaccharides that sugar is made up of three monosaccharide units two glycosidic bonds generates three molecule monosaccharide, such as gossypose after hydrolysis.Polysaccharide
It is polymerized by 10 or more monosaccharide molecules.Multiple monosaccharide or oligosaccharide are produced after hydrolysis.According to generating monosaccharide after hydrolysis
Composition it is whether identical, can be divided into: homopolysaccharide is made of a kind of monosaccharide, and monosaccharide of the same race is generated after hydrolysis.As Arabic gum,
Glycogen, starch, cellulose etc..Heteromeric polysaccharide is made of a variety of monosaccharide, and different types of monosaccharide is generated after hydrolysis.As mucopolysaccharide,
Hemicellulose etc..Glycoconjugate (complex carbohydrate, glycoconjugate), the reducing end and protein of carbohydrate or
The product of lipid binding.
The hydrolysate monosaccharide of polysaccharide and cellulose is in many field extensive applications.Polysaccharide hydrolysis mainly uses at present
Bronsted acid or metal-supported catalyst, seriously polluted or higher cost.Attapulgite has large specific surface area, thermostabilization
Property it is good, surface silanol groups in acidity, acid catalysis field have be widely applied.Polysaccharide water is catalyzed using recessed native stick stone as precursor
Solution, has many advantages, such as that environmentally protective, catalyst is reusable, and is of great significance to pushing Mineral Resources in China to develop.
Summary of the invention
The purpose of the present invention is to provide a kind of economical and eco-friendly saccharide compound method for hydrolysis, this process environment is friendly,
Mild condition, catalyst are reusable, seriously polluted in prior art to overcome, and energy consumption is high, and catalyst is not easily recycled, is secondary anti-
Answer the disadvantages of more.
To achieve the above object, The technical solution adopted by the invention is as follows:
The present invention provides a kind of method for hydrolysis of saccharide compound, and the saccharide compound is oligosaccharide or/and polysaccharide, is somebody's turn to do
Method for hydrolysis are as follows: by solid acid catalyst and saccharide compound hybrid reaction in water, 40-250 DEG C of reaction temperature, the reaction time
It is 0.1-72h to get monosaccharide compounds.
Preferred oligosaccharide of the present invention is disaccharides, trisaccharide or tetrose, wherein the disaccharides be melibiose, kojibiose,
Mannobiose, nigerose, gentiobiose, xylobiose, trehalose, laminaribiose, turanose, lactose, maltose, sucrose or
Cellobiose；The trisaccharide is to hide fruit trisaccharide, maltotriose, raffinose, melezitose, Chinese herbaceous peony trisaccharide；The tetrose is wood four
Sugar, maltotetraose, Nystose, cellotetrose.
Preferred polysaccharide of the present invention is fructooligosaccharide, inulin, cellulose or starch.
The aqueous solution mass concentration of preferred saccharide compound of the present invention is 0.1-100%.
The mass ratio of preferred solid acid catalyst and saccharide compound of the present invention is 1:1-1:1000.
Preferred solid acid catalyst of the present invention is attapulgite catalyst, with preceding in 100-1000 DEG C of work
Change.
The present invention also provides a kind of preparation methods of attapulgite catalyst, before which is with attapulgite
Body obtains its acidity modification through Bronsted acid or other active components.
Preferred Bronsted acid of the present invention is acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid；The concentration of Bronsted acid is 0.1-
10mol/L, processing time are 1 hour to 72 hours.
Preferred other active components of the present invention are nickel, tungsten, titanium, zirconium, chromium, aluminium, cobalt, platinum, palladium, ruthenium, molybdenum, vanadium, tin
One of or it is a variety of；The mass ratio of other active components and attapulgite clay is 0.1%-50%.
The present invention also provides a kind of application of attapulgite catalyst in the hydrolysis of saccharide compound, the sugar
Class compound is oligosaccharide or/and polysaccharide.
The present invention has the advantage that
1, compared with traditional bronsted acid catalyst polysaccharide hydrolysis method, the solid acid catalyst activity that the present invention uses is high,
There is good selectivity to product, it is environmental-friendly, it is not soluble in water, it is easily isolated, does not easily cause equipment to corrode, catalyst is at low cost
It is honest and clean.
2, not only economical and easily available using natural minerals attapulgite clay as catalyst precarsor, but also mineral products money can be promoted
The added value in source pushes the development and utilization of Mineral Resources in China.
3, catalyst separation is simple, reusable, and catalytic efficiency is without being substantially reduced.
Specific embodiment
The present invention will be explained in further detail in the following example, but the contents of the present invention are not limited thereto.
Embodiment 1
Attapulgite 1.5g is taken, prepared 1M sulfuric acid 20ml is added, 52h is stirred at room temperature, stands aging 12h, from
The heart isolates lower sediment thing, is then washed with water to pH into neutrality, 60 DEG C of dryings, grinding, and later in a vacuum drying oven 110
DEG C dry 2h is to slowly warm up to 300 DEG C of activation 3h in Muffle furnace to get to required catalyst, is to handle through phosphoric acid
Attapulgite catalyst.
Take it is above-mentioned it is sulfuric acid-treated after obtain attapulgite catalyst 0.1g, inulin 1.2g, be added 20ml water, 60 DEG C
60min is reacted, reaction solution is filtered to isolate into catalyst, measures monosaccharide yield 98%.By washing and drying after catalyst recycling
It can continue cycling through use, cycle-index 3 times or more.
Embodiment 2
Attapulgite 1.5g is taken, prepared 1.5M phosphoric acid 20ml is added, 52h is stirred at room temperature, stands aging 12h,
It is centrifugated out lower sediment thing, is then washed with water to pH into neutrality, 60 DEG C of dryings are ground, later in a vacuum drying oven
110 DEG C of dry 2h are to slowly warm up to 300 DEG C of activation 3h to get required catalyst is arrived, to handle through phosphoric acid in Muffle furnace
Attapulgite catalyst.
Take it is above-mentioned obtain attapulgite catalyst 0.1g, cellobiose 1.2g after phosphoric acid is handled, 20ml water is added,
90 DEG C of reaction 60min, filter to isolate catalyst for reaction solution, measure monosaccharide yield 95%.
Embodiment 3
Attapulgite 1.5g is taken, prepared 3M hydrochloric acid 20ml is added, 52h is stirred at room temperature, stands aging 12h, from
The heart isolates lower sediment thing, is then washed with water to pH into neutrality, 60 DEG C of dryings, grinding, and later in a vacuum drying oven 110
DEG C dry 2h is to slowly warm up to 300 DEG C of activation 3h in Muffle furnace to get to required catalyst, is through HCl treatment
Attapulgite catalyst.
Take it is above-mentioned obtain attapulgite catalyst 0.1g, sucrose 1.2g after HCl treatment, be added 20ml water, 80 DEG C
270min is reacted, reaction solution is filtered to isolate into catalyst, measures monosaccharide yield 91%.
Embodiment 4
By the catalyst Maltose hydrolysis in embodiment 3: catalyst 0.2g, maltose 4g add water 30ml, and 120 DEG C
It is stirred to react 5h, glucose yield 96%.
Embodiment 5
The catalyst that catalyst in Example 2 is hydrolyzed as melezitose.Catalyst 0.2g, melezitose 6g are added into water
40ml, 120 DEG C are stirred to react 6h, glucose yield 89%.
Embodiment 6
Attapulgite 1.5g is taken, prepared 3M acetic acid 20ml is added, 52h is stirred at room temperature, stands aging 12h, from
The heart isolates lower sediment thing, is then washed with water to pH into neutrality, 60 DEG C of dryings, grinding, and later in a vacuum drying oven 110
DEG C dry 2h is to slowly warm up to 300 DEG C of activation 3h in Muffle furnace to get to required catalyst, is through acetic acid treatment
Attapulgite catalyst.
Take it is above-mentioned obtain attapulgite catalyst 0.1g, sucrose 1.2g after acetic acid treatment, be added 40ml water, 80 DEG C
5h is reacted, reaction solution is filtered to isolate into catalyst, measures monosaccharide yield 91%.
Embodiment 7
Catalyst Starch Hydrolysis in Example 1, catalytic condition are as follows: catalyst 0.1g, starch 1.2g, are added
40ml water, 130 DEG C of reaction 5h, filters to isolate catalyst for reaction solution, measures monosaccharide yield 80%.
Influence of the acid processing to attapulgite clay catalytic performance
Comparative example 1: taking attapulgite clay 0.2g, and distilled water 20ml is added in reaction kettle in starch 1.0g, and 130 DEG C anti-
5h is answered, measuring Starch Hydrolysis rate is 2.6%.By gained catalyst 0.2g after attapulgite clay 1M sulfuric acid treatment, catalysis is formed sediment
Distilled water 20ml, 130 DEG C of reaction 5h are added in reaction kettle in powder 1.0g, and measuring Starch Hydrolysis rate is 89.6%.
Before and after the processing, Starch Hydrolysis rate is from 2.6% for attapulgite clay acid it can be seen from the experimental result of comparative example 1
It has been increased to 89.6%, it can be seen that sulfuric acid treatment can greatly improve the effect of attapulgite clay catalyst Polysaccharides
Fruit.
Comparative example 2: taking attapulgite clay 0.5g, and distilled water 40ml, 90 DEG C of reactions are added in reaction kettle in inulin 1.0g
5h, measuring hydrolysis of inulin rate is 4.7%.By attapulgite clay 0.5g, with 1M sulfuric acid treatment 3h, 500 DEG C of activation take gained to urge
Distilled water 40ml, 75 DEG C of reaction 2.5h are added in agent 0.5g, inulin 1.0g, and measuring hydrolysis of inulin rate is 99.8%.
With 1M sulfuric acid treatment 3h it can be seen from the experimental result of comparative example 2,500 DEG C are activated obtained concave convex rod
Stone clay catalyst, the temperature of hydrolytic inulin is relatively low, the reaction time is short, and percent hydrolysis is up to 99.8%, and is conducive to save
The energy reduces production cost.
It can be seen from the above embodiments that, the present invention is using attapulgite as catalyst precarsor, by difference
Bronsted acid is modified, and realization compound of polysaccharide Efficient Conversion is monosaccharide.Protic Acid Catalyzed process is compared, catalytic process green
Pollution-free, catalyst is reusable, shows good prospects for commercial application.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from of the invention
In the case where spirit and scope, embodiments of the present invention can be made with various changes, replacement and change.
Claims (10)
1. a kind of method for hydrolysis of saccharide compound, which is characterized in that the saccharide compound is oligosaccharide or/and polysaccharide, is somebody's turn to do
Method for hydrolysis are as follows: by solid acid catalyst and saccharide compound hybrid reaction in water, 40-250 DEG C of reaction temperature, the reaction time
It is 0.1-72h to get monosaccharide compounds.
2. method for hydrolysis according to claim 1, which is characterized in that the oligosaccharide be disaccharides, trisaccharide or tetrose, wherein
The disaccharides be melibiose, kojibiose, mannobiose, nigerose, gentiobiose, xylobiose, trehalose, laminaribiose,
Turanose, lactose, maltose, sucrose or cellobiose；The trisaccharide be ketose, maltotriose, raffinose, melezitose,
Chinese herbaceous peony trisaccharide；The tetrose is stachyose, maltotetraose, Nystose, cellotetrose.
3. method for hydrolysis according to claim 1, which is characterized in that the polysaccharide is fructooligosaccharide, inulin, cellulose or shallow lake
Powder.
4. method for hydrolysis according to claim 1, which is characterized in that the aqueous solution mass concentration of the saccharide compound is
0.1-100%.
5. method for hydrolysis according to claim 1, which is characterized in that the matter of the solid acid catalyst and saccharide compound
Amount ratio is 1:1-1:1000.
6. method for hydrolysis according to claim 1-5, which is characterized in that the solid acid catalyst is recessed native stick
Stone clay catalyst is activated with preceding at 100-1000 DEG C.
7. a kind of preparation method of attapulgite catalyst, which is characterized in that the catalyst is using attapulgite as precursor, warp
Bronsted acid or other active components obtain its acidity modification.
8. preparation method according to claim 7, which is characterized in that the Bronsted acid is acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid
Or nitric acid；The concentration of Bronsted acid is 0.1-10mol/L, and the processing time is 1 hour to 72 hours.
9. preparation method according to claim 7, which is characterized in that other described active components be nickel, tungsten, titanium, zirconium,
Chromium, aluminium, cobalt, platinum, palladium, ruthenium, molybdenum, one of vanadium, tin or a variety of；The mass ratio of other active components and attapulgite clay is
0.1%-50%.
10. according to the attapulgite catalyst of any one of the claim 7-9 preparation method preparation in saccharide compound
Hydrolysis in application, the saccharide compound be oligosaccharide or/and polysaccharide.
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| CN201810803458.9A CN108950090A (en) | 2018-07-20 | 2018-07-20 | A kind of method for hydrolysis of saccharide compound |
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| CN201810803458.9A CN108950090A (en) | 2018-07-20 | 2018-07-20 | A kind of method for hydrolysis of saccharide compound |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111893219A (en) * | 2020-07-14 | 2020-11-06 | 江苏理工学院 | Method for catalyzing hydrolysis of polysaccharide by carbon-based solid acid catalyst |
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| CN1927874A (en) * | 2006-09-27 | 2007-03-14 | 华东理工大学 | Method and apparatus for preparing monosaccharide with diluent acid continuous catalyzing biomass |
| CN103509886A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method and catalyst for hydrolyzing saccharide compounds |
| CN106345491A (en) * | 2016-07-29 | 2017-01-25 | 中国科学院广州能源研究所 | Grafted solid acid catalyst, preparation method thereof and application of grafted solid acid catalyst in saccharification process of lignocellulose |
| CN108164481A (en) * | 2018-01-03 | 2018-06-15 | 江苏理工学院 | A kind of preparation method of 5 hydroxymethyl furfural |
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2018
- 2018-07-20 CN CN201810803458.9A patent/CN108950090A/en active Pending
Patent Citations (4)
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| CN1927874A (en) * | 2006-09-27 | 2007-03-14 | 华东理工大学 | Method and apparatus for preparing monosaccharide with diluent acid continuous catalyzing biomass |
| CN103509886A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method and catalyst for hydrolyzing saccharide compounds |
| CN106345491A (en) * | 2016-07-29 | 2017-01-25 | 中国科学院广州能源研究所 | Grafted solid acid catalyst, preparation method thereof and application of grafted solid acid catalyst in saccharification process of lignocellulose |
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| CN111893219A (en) * | 2020-07-14 | 2020-11-06 | 江苏理工学院 | Method for catalyzing hydrolysis of polysaccharide by carbon-based solid acid catalyst |
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Application publication date: 20181207 |