CN104946803A - Method for preparing xylose hydrolysis fluid by utilizing oxalic acid mixed ball milling pretreated corncob - Google Patents
Method for preparing xylose hydrolysis fluid by utilizing oxalic acid mixed ball milling pretreated corncob Download PDFInfo
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- CN104946803A CN104946803A CN201510278766.0A CN201510278766A CN104946803A CN 104946803 A CN104946803 A CN 104946803A CN 201510278766 A CN201510278766 A CN 201510278766A CN 104946803 A CN104946803 A CN 104946803A
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- ball milling
- oxalic acid
- corn cob
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- xylose hydrolysis
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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
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/002—Xylose
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Abstract
The invention belongs to the technical field of preparation of biomass chemicals and discloses a method for preparing a xylose hydrolysis fluid by utilizing oxalic acid mixed ball milling pretreated corncob. The method for preparing the xylose hydrolysis fluid by utilizing the oxalic acid mixed ball milling pretreated corncob comprises the following operation steps: (1) crushing and sieving corncob, mixing sieved corncob with an oxalic acid solution, and then carrying out ball milling pre-treatment on a mixture; and (2) adding water into the mixture subjected to the ball milling pre-treatment, carrying out ultrasonic treatment, then carrying out hydrothermal pre-treatment reaction in a microwave reaction kettle, cooling after reaction is finished, and carrying out centrifugal separation to obtain the xylose hydrolysis fluid and solid residue rich in cellulose and lignin. The method for preparing the xylose hydrolysis fluid by utilizing the oxalic acid mixed ball milling pretreated corncob has the advantages of environment-friendly technology, high xylose yield and low byproduct content and has a good application prospect.
Description
Technical field
The invention belongs to biomass chemical preparing technical field, be specifically related to a kind of method that oxalic acid mixing and ball milling pre-treatment corn cob prepares xylose hydrolysis fluid.
Background technology
Along with the progressively deterioration of the day by day exhausted of fossil energy and environment for human survival, the energy that the mankind face and environmental problem increasingly severe.Thus, mouse out one and can replace fossil resources, and there is renewable and eco-friendly novel energy seem extremely urgent.Based on the biomass resource of agriculture and forestry plant resource, obtaining different kind organism mass-energy source, biomass platform chemicals and biomass type material by the processing of different approach, is the Main way of researcher and production development personnel research and development now.
Wood sugar, as a kind of sugar of empty calory, is the reasonable carbohydrate of physiologically active in all table sugar.Wood sugar not increasing blood glucose value because having, being conducive to the features such as bifidus bacillus, and shows the performance being better than other carbohydrates.In addition wood sugar can also reduce free fatty acids in body, adjustment human body lipid metabolism, liking extensively by obesity and diabetic subject.Another important purposes of wood sugar is as the important intermediate chemical of chemical industry, in order to prepare the higher Chemicals of added value, as furfural and Xylitol etc.In addition wood sugar also has purposes widely in the industry such as leather, dyestuff, spices.
The nineties in last century, wood sugar has obtained in developed country and has used widely.The main preparation methods of wood sugar is mineral acid hydrolysis agriculture and forestry plant fiber wastes, and the common agriculture and forestry plant fiber wastes being rich in wood sugar has corn cob, bagasse, cotton seed hulls, rice husk etc.Wherein corn cob there are wide material sources, be easy to process, feature that xylose yield is high.
Present major part research still rests on the stage of dilute mineral acid hydrolysis agriculture and forestry plant fiber wastes, what the method was difficult to avoid runs into a lot of puzzlement, such as mineral acid is to the corrosive nature of equipment, mineral acid is difficult to recycling after hydrolyzed, and the strongly-acid of mineral acid causes by product in hydrolyzed solution too much.
Summary of the invention
In order to solve the shortcoming and defect part of prior art, a kind of oxalic acid mixing and ball milling pre-treatment corn cob is the object of the present invention is to provide to prepare the method for xylose hydrolysis fluid.
The object of the invention is achieved through the following technical solutions:
Oxalic acid mixing and ball milling pre-treatment corn cob prepares a method for xylose hydrolysis fluid, comprises following operation steps:
(1) corn cob is ground screening, the corn cob after screening mixes with oxalic acid solution, then mixture is carried out ball milling pretreatment;
(2) add water the mixture after ball milling pretreatment also supersound process, and then in microwave reaction kettle, carry out hydrothermal pretreatment reaction, reaction terminates rear cooling, and centrifugation obtains the solid residue of xylose hydrolysis fluid and rich cellulose and lignin.
Preferably, the order number grinding the corn cob of screening described in step (1) is 20 ~ 60 orders;
Preferably, the concentration of step (1) mesoxalic acid solution is 0.6 ~ 0.8mol/L, and the add-on of oxalic acid solution and the liquid-solid ratio (mL:g) of corn cob add-on are (3 ~ 5): 10.
Preferably, the condition of the ball milling pretreatment described in step (1) is: rotational speed of ball-mill 300 ~ 400r/min, and mill bead footpath is 0.5 ~ 1cm, and mill pearl quantity is 12 ~ 16, and Ball-milling Time is 1 ~ 3h.
Preferably, the add-on of water described in step (2) is (10 ~ 30) with the liquid-solid ratio (mL:g) with corn cob add-on: 1.
Preferably, described in step (2), the condition of supersound process is: ultrasonic power 30 ~ 40KHz, and sonication treatment time is 20 ~ 40min.
Preferably, in microwave reaction kettle described in step (2), the power of microwave is 400 ~ 600W; The heating rate of microwave is 10 ~ 30 DEG C/min.
Preferably, the reaction of hydrothermal pretreatment described in step (2) refers to reaction 10 ~ 30min under temperature is 130 ~ 150 DEG C of conditions.
The present invention realizes hemicellulose efficient catalytic in total composition biomass mainly through two steps and is converted into wood sugar; First the pre-treatment of oxalic acid mixing and ball milling is carried out to corn cob; Then under microwave condition, the hydrolyzed solution that the hydrolysis of rare organic acid hydrothermal pretreatment obtains being rich in wood sugar is carried out to corn cob.Relative to mineral acid hydrolysis, in the process of hemicellulose degradation, oxalic acid has excellent bionic catalysis performance.Simultaneously because the acidity quotient of oxalic acid is higher, under equal conditions, the demand concentration of hydrolytic process mesoxalic acid is well below mineral acid, therefore greatly reduces the possibility that equipment corrosion occurs.Oxalic acid also has a unrivaled performance can be recycled by recrystallization in hydrolyzed solution exactly.Ball milling is as a kind of pretreated method of common Physical, its feature is, effectively reduce the size of plant fiber material, increase the surface-area of plant fiber material simultaneously, the degree of crystallinity of fibrous material can also be reduced efficiently, the great like this close contact facilitating chemical and fibrous material in preprocessing process.And by oxalic acid and the blended ball milling of corn cob, its role is to mechanical milling process mesoxalic acid can enter in the cell walls of corn cob, fully contact with hemicellulose, thus improve the yield of wood sugar greatly.
Preparation method of the present invention and the product tool obtained have the following advantages and beneficial effect:
(1) the method for the invention does not relate to adding of mineral acid, but have employed organic acid oxalic acid, avoids equipment corrosion, and oxalic acid can be reclaimed by recrystallization method;
(2) the present invention adopts oxalic acid and the blended ball milling of corn cob, can enter in the cell walls of corn cob, fully contact and react with hemicellulose at mechanical milling process mesoxalic acid, improves wood sugar yield;
(3) the present invention adopts the method for microwave heating, can compared with low reaction temperatures, obtain higher xylose yield in the shorter reaction time, and effectively avoid the generation of by product, the purity of xylose hydrolysis fluid is higher simultaneously.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
In following examples gained xylose hydrolysis fluid, the concentration of wood sugar adopts high performance liquid chromatography to measure;
In following examples gained xylose hydrolysis fluid in wood sugar yield=hydrolyzed solution wood sugar concentration × hydrolysis before add the content of volume/1g corn cob Raw half fiber of water.
Embodiment 1
A kind of oxalic acid mixing and ball milling pre-treatment corn cob of the present embodiment prepares the method for xylose hydrolysis fluid, and concrete preparation process is as follows:
(1) corn cob is ground be sized to 20 orders after get 1g, the oxalic acid solution being 0.6mol/L with 0.3mL concentration mixes in ball grinder, adds the mill pearl that 12 particle diameters are 0.5cm, ball milling 1h under the speed conditions of 300r/min.
(2) corn cob after ball milling is all transferred in microwave reaction tank, add the deionized water of 10mL simultaneously, ultrasonic 20min under the ultrasound condition of 30kHz.Arranging microwave temperature rise rate after closing microwave reaction tank is 10 DEG C/min, and final holding temperature is 130 DEG C, insulation duration and reaction times 10min.After reaction terminates, be cooled to room temperature, obtain the solid residue of xylose hydrolysis fluid and rich cellulose and lignin through centrifugation.
It is 85% that the xylose hydrolysis fluid that the present embodiment obtains calculates wood sugar yield after measuring xylose concentration.
Embodiment 2
A kind of oxalic acid mixing and ball milling pre-treatment corn cob of the present embodiment prepares the method for xylose hydrolysis fluid, and concrete preparation process is as follows:
(1) corn cob is ground be sized to 40 orders after get 1g, the oxalic acid solution being 0.7mol/L with 0.4mL concentration mixes in ball grinder, adds the mill pearl that 14 particle diameters are 0.8cm, ball milling 2h under the speed conditions of 350r/min.
(2) corn cob after ball milling is all transferred in microwave reaction tank, add the deionized water of 20mL simultaneously, ultrasonic 30min under the ultrasound condition of 35kHz.Arranging microwave temperature rise rate after closing microwave reaction tank is 20 DEG C/min, and final holding temperature is 140 DEG C, insulation duration and reaction times 20min.After reaction terminates, be cooled to room temperature, obtain the solid residue of xylose hydrolysis fluid and rich cellulose and lignin through centrifugation.
It is 95% that the xylose hydrolysis fluid that the present embodiment obtains calculates wood sugar yield after measuring xylose concentration.
Embodiment 3
A kind of oxalic acid mixing and ball milling pre-treatment corn cob of the present embodiment prepares the method for xylose hydrolysis fluid, and concrete preparation process is as follows:
(1) corn cob is ground be sized to 60 orders after get 1g, the oxalic acid solution being 0.8mol/L with 0.5mL concentration mixes in ball grinder, adds the mill pearl that 14 particle diameters are 1cm, ball milling 3h under the speed conditions of 400r/min.
(2) corn cob after ball milling is all transferred in microwave reaction tank, add the deionized water of 30mL simultaneously, ultrasonic 40min under the ultrasound condition of 40kHz.Arranging microwave temperature rise rate after closing microwave reaction tank is 30 DEG C/min, and final holding temperature is 150 DEG C, insulation duration and reaction times 30min.After reaction terminates, be cooled to room temperature, obtain the solid residue of xylose hydrolysis fluid and rich cellulose and lignin through centrifugation.
It is 90% that the xylose hydrolysis fluid that the present embodiment obtains calculates wood sugar yield after measuring xylose concentration.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. oxalic acid mixing and ball milling pre-treatment corn cob prepares a method for xylose hydrolysis fluid, it is characterized in that: comprise following operation steps:
(1) corn cob is ground screening, the corn cob after screening mixes with oxalic acid solution, then mixture is carried out ball milling pretreatment;
(2) add water the mixture after ball milling pretreatment also supersound process, and then in microwave reaction kettle, carry out hydrothermal pretreatment reaction, reaction terminates rear cooling, and centrifugation obtains the solid residue of xylose hydrolysis fluid and rich cellulose and lignin.
2. a kind of oxalic acid mixing and ball milling pre-treatment corn cob according to claim 1 prepares the method for xylose hydrolysis fluid, it is characterized in that: the order number grinding the corn cob of screening described in step (1) is 20 ~ 60 orders.
3. a kind of oxalic acid mixing and ball milling pre-treatment corn cob according to claim 1 prepares the method for xylose hydrolysis fluid, it is characterized in that: described in step (1), the concentration of oxalic acid solution is 0.6 ~ 0.8mol/L, the liquid-solid ratio of oxalic acid solution add-on and corn cob add-on is (3 ~ 5): 10.
4. a kind of oxalic acid mixing and ball milling pre-treatment corn cob according to claim 1 prepares the method for xylose hydrolysis fluid, it is characterized in that: the condition of the ball milling pretreatment described in step (1) is: rotational speed of ball-mill 300 ~ 400r/min, mill bead footpath is 0.5 ~ 1cm, mill pearl quantity is 12 ~ 16, and Ball-milling Time is 1 ~ 3h.
5. a kind of oxalic acid mixing and ball milling pre-treatment corn cob according to claim 1 prepares the method for xylose hydrolysis fluid, it is characterized in that: the add-on of water described in step (2) is (10 ~ 30) with the liquid-solid ratio with corn cob add-on: 1.
6. a kind of oxalic acid mixing and ball milling pre-treatment corn cob according to claim 1 prepares the method for xylose hydrolysis fluid, it is characterized in that: described in step (2), the condition of supersound process is: ultrasonic power 30 ~ 40KHz, sonication treatment time is 20 ~ 40min.
7. a kind of oxalic acid mixing and ball milling pre-treatment corn cob according to claim 1 prepares the method for xylose hydrolysis fluid, it is characterized in that: in microwave reaction kettle described in step (2), the power of microwave is 400 ~ 600W; The heating rate of microwave is 10 ~ 30 DEG C/min.
8. a kind of oxalic acid mixing and ball milling pre-treatment corn cob according to claim 1 prepares the method for xylose hydrolysis fluid, it is characterized in that: the reaction of hydrothermal pretreatment described in step (2) refers to reaction 10 ~ 30min under temperature is 130 ~ 150 DEG C of conditions.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498801A (en) * | 2015-12-29 | 2016-04-20 | 华南理工大学 | Preparation method of sulfated carbonized corn cob catalyst and method for preparing furfural from xylose in presence of catalyst |
| CN105803120A (en) * | 2016-03-25 | 2016-07-27 | 浙江工业大学 | Method for preparing xylose hydrolysate by hydrolyzing corn cobs with mixed acid |
| CN107267688A (en) * | 2017-07-03 | 2017-10-20 | 南京工业大学 | A kind of method that utilization mill grinding prepares xylo-oligosaccharide or xylose |
| CN109097502A (en) * | 2018-07-23 | 2018-12-28 | 华南理工大学 | A method of the oxalic acid pretreatment wood fibre that can be recycled prepares xylose |
| CN110205412A (en) * | 2018-02-28 | 2019-09-06 | 中国科学院大连化学物理研究所 | A kind of non-enzyme-cellulose hydrolysis and saccharification technology |
| CN112210575A (en) * | 2020-11-05 | 2021-01-12 | 浙江科技学院 | Process for preparing xylose by using tea leaves |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498801A (en) * | 2015-12-29 | 2016-04-20 | 华南理工大学 | Preparation method of sulfated carbonized corn cob catalyst and method for preparing furfural from xylose in presence of catalyst |
| CN105803120A (en) * | 2016-03-25 | 2016-07-27 | 浙江工业大学 | Method for preparing xylose hydrolysate by hydrolyzing corn cobs with mixed acid |
| CN107267688A (en) * | 2017-07-03 | 2017-10-20 | 南京工业大学 | A kind of method that utilization mill grinding prepares xylo-oligosaccharide or xylose |
| CN107267688B (en) * | 2017-07-03 | 2018-06-29 | 南京工业大学 | A kind of method that xylo-oligosaccharide or xylose are prepared using mill grinding |
| CN110205412A (en) * | 2018-02-28 | 2019-09-06 | 中国科学院大连化学物理研究所 | A kind of non-enzyme-cellulose hydrolysis and saccharification technology |
| CN110205412B (en) * | 2018-02-28 | 2022-03-18 | 中国科学院大连化学物理研究所 | Method for preparing glucose by hydrolyzing and saccharifying non-enzymatic cellulose |
| CN109097502A (en) * | 2018-07-23 | 2018-12-28 | 华南理工大学 | A method of the oxalic acid pretreatment wood fibre that can be recycled prepares xylose |
| CN109097502B (en) * | 2018-07-23 | 2021-08-10 | 华南理工大学 | Method for preparing xylose by pretreating wood fiber with oxalic acid capable of being recycled |
| CN112210575A (en) * | 2020-11-05 | 2021-01-12 | 浙江科技学院 | Process for preparing xylose by using tea leaves |
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