CN102392378B - Method for catalytically preparing bagasse microcrystalline cellulose by carbon dioxide - Google Patents
Method for catalytically preparing bagasse microcrystalline cellulose by carbon dioxide Download PDFInfo
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- CN102392378B CN102392378B CN201110230523.1A CN201110230523A CN102392378B CN 102392378 B CN102392378 B CN 102392378B CN 201110230523 A CN201110230523 A CN 201110230523A CN 102392378 B CN102392378 B CN 102392378B
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Abstract
The invention relates to a method for catalytically degrading bagasse cellulose and preparing microcrystalline cellulose by carbon dioxide, which comprises the following steps of: using bagasse cellulose pulp obtained in a way that utilizing bagasse to making pulp so as to make paper and deionized water as raw materials and taking subcritical water as reaction mediums and CO2 as a catalyst. The method has the beneficial effects that the process is simple, the source of the used raw materials is wide, the cost is low, the polymerization degree of the obtained bagasse microcrystalline cellulose is 50-300; products are clean and are not polluted, three wastes are not discharged in the whole process, and the significance is important in view of energy conservation, emission reduction and atom economy.
Description
Technical field
The present invention relates to a kind of polymeric material field of preparing, especially belong to the method for preparing microcrystalline cellulose.
Background technology
Native cellulose is the abundantest in the world macromolecule organic material, is the noticeable field of current field of new developmental research.Increasingly the exhaustion of oil causes petroleum price in recent years to rise steadily, and along with the mankind see clearly the negative effect that oil brings environment and human health gradually, the mankind pay close attention to this renewable resource of cellulose more.Yet cellulosic chemical property is highly stable, this has seriously restricted cellulosic application.To cellulose degradation, deep processing is to obtain the focus that industrial chemicals and intermediate are various countries' research always.
Microcrystalline cellulose is through the reach capacity polysaccharose substance of the degree of polymerization of degraded by native cellulose.Because tool is of use in many ways and good performance, food, cosmetics, medicine and synthetic leather field have now been widely used in.Since nineteen seventies, China produces with application aspect and constantly makes further progress at microcrystalline cellulose.Yet, and abroad compare, the microcrystalline cellulose product of China, on kind, Yield and quality and application approach thereof, all there is a big difference.The PH300 series that for example U.S. FMC produces is much better than China's product, for this new product is developed rapidly at home, dwindle and external gap, China must improve and study, the needs that comprehensively increase to meet national economy at aspects such as production method and technology, product quality and kinds.
The microcrystalline cellulose that various countries produce, of a great variety, character differs, and the raw material adopting, process conditions and equipment are also not quite similar.But it mainly manufactures principle and basic technology route or consistent, adopt the chemical processes such as acid hydrolysis, washing, dry, pulverizing to manufacture microcrystalline cellulose.The method of suitability for industrialized production mainly contains chemical method, Mechanical Method at present, and also having microbe fermentation method is in addition that enzymatic isolation method is just in research and development process.
In order further to realize market efficiency, people utilize more cheap raw material and the method for more environmental protection to prepare microcrystalline cellulose continuous exploration.Bagasse is the discarded object that sugar refinery produces, and contains abundant native cellulose, and bagasse is mainly as fuel and papermaking at present.By degraded bagasse cellulose, produce the microcrystalline cellulose product of high added value, will realize the higher value application of bagasse.Guangxi is to produce the large province of sugar, has a large amount of bagasse resources, and therefore developing cellulosic processing has advantageous condition.Traditional production line of preparing microcrystalline cellulose by bagasse is: bagasse → preliminary treatment → add hydrochloric acid, auxiliary agent are hydrolyzed → add water, deashing agent washs → be dried, makes powder → product.This kind of method prepared bagasse microcrystalline cellulose, and owing to using strong acid as catalyst, equipment corrosion is serious.In addition, the discharge containing acid waste liquid pollutes surrounding environment.The present invention be take subcritical water as reaction media, CO
2for catalyst degraded bagasse, prepare microcrystalline cellulose, technique is simple, and the raw material sources of employing are extensive, with low cost, product cleanliness without any pollution, and whole process three-waste free discharge, the green chemical industry of realizing is truly produced.
Subcritical water refers to temperature higher than its boiling point but lower than critical-temperature, and pressure is lower than the aqueous water of its critical pressure.[H in subcritical water
3o
+] and [OH
-] approached weak acid or weak base, at saturated vapour, to depress, the dissociation constant of subcritical water has a maximum to be about 10 near 260 ℃
-11(mol/kg)
2, its value is 1000 times of normal temperature and pressure water, and dissociation constant increases with the increase of pressure, so self has the function of acid catalysis and base catalysis.In subcritical water system, be filled with CO
2gas, can provide pressure to system on the one hand, increases the dissociation constant of subcritical water; On the other hand, be dissolved in the CO in subcritical water
2can generate H
2cO
3, H
2cO
3[the H ionizing out
3o
+] can increase again the hydrogen ion concentration of system, further promote acid catalyzed effect.The native cellulose of degrading in subcritical water, can not only prepare the microcrystalline cellulose of cleanliness without any pollution and pollution abatement from source in industrial production.
Summary of the invention
A kind of method of preparing bagasse microcrystalline cellulose that the object of this invention is to provide cleanliness without any pollution, whole process three-waste free discharge, it can overcome the shortcoming that the strong acid as catalyst of existing use is prepared Microcrystalline Celulose from Sugar Cane Slag.
The method that the present invention prepares bagasse microcrystalline cellulose is to take the subcritical water of 140～250 ℃ as reaction media, at CO
2under the catalysis of gas, realize, technique comprises the steps:
(1) raw material is processed: by bagasse cellulose pulp and deionization, be 1: 10～100 fully to mix by weight, soak 10～60 minutes, pack in autoclave;
(2) high-temperature high-voltage reaction: pass into CO
2in displacement still, after air, be filled with the CO of 0.5～10MPa
2gas, reaction temperature is 140～250 ℃, the reaction time is 10～180 minutes;
(3) product purification: through centrifugation, bleaching, dry, pulverization process, obtain lily bagasse microcrystalline cellulose.
The inventive method is simple, and the bagasse microcrystalline cellulose color and luster obtaining is pure white, and the degree of polymerization is 50～300, and product can be for fields such as food industry, daily-use chemical industry and light industrys.
The specific embodiment
The method of describing for further illustrating the present invention by concrete embodiment below, but do not limit the present invention.
Embodiment 1
Accurately take bagasse cellulose pulp 10g, add deionized water 100g, after fully mixing, soak 10 minutes, pack in autoclave.Pass into CO
2in displacement still, after air, be filled with the CO of 0.5MPa
2gas reacts 180 minutes at 140 ℃.After reaction finishes, shift out autoclave cooling, open kettle cover, pour out mixed liquor, centrifugal, pour out supernatant liquid, the solid obtaining is bagasse microcrystalline cellulose.To thick product bleach, wash, filter, be dried, pulverization process, obtain lily bagasse microcrystalline cellulose, the degree of polymerization is 298.
Embodiment 2
Accurately take bagasse cellulose pulp 10g, add deionized water 200g, after fully mixing, soak 20 minutes, pack in autoclave.Pass into CO
2in displacement still, after air, be filled with the CO of 2.0MPa
2gas reacts 150 minutes at 160 ℃.After reaction finishes, shift out autoclave cooling, open kettle cover, pour out mixed liquor, centrifugal, pour out supernatant liquid, the solid obtaining is bagasse microcrystalline cellulose.To thick product bleach, wash, filter, be dried, pulverization process, obtain lily bagasse microcrystalline cellulose, the degree of polymerization is 263.
Embodiment 3
Accurately take bagasse cellulose pulp 10g, add deionized water 400g, after fully mixing, soak 30 minutes, pack in autoclave.Pass into CO
2in displacement still, after air, be filled with the CO of 4.0MPa
2gas reacts 120 minutes at 180 ℃.After reaction finishes, shift out autoclave cooling, open kettle cover, pour out mixed liquor, centrifugal, pour out supernatant liquid, the solid obtaining is bagasse microcrystalline cellulose.To thick product bleach, wash, filter, be dried, pulverization process, obtain lily bagasse microcrystalline cellulose, the degree of polymerization is 246.
Embodiment 4
Accurately take bagasse cellulose pulp 10g, add deionized water 500g, after fully mixing, soak 40 minutes, pack in autoclave.Pass into CO
2in displacement still, after air, be filled with the CO of 6.0MPa
2gas reacts 90 minutes at 200 ℃.After reaction finishes, shift out autoclave cooling, open kettle cover, pour out mixed liquor, centrifugal, pour out supernatant liquid, the solid obtaining is bagasse microcrystalline cellulose.To thick product bleach, wash, filter, be dried, pulverization process, obtain lily bagasse microcrystalline cellulose, the degree of polymerization is 181.
Embodiment 5
Accurately take bagasse cellulose pulp 10g, add deionized water 600g, after fully mixing, soak 50 minutes, pack in autoclave.Pass into CO
2in displacement still, after air, be filled with the CO of 8.0MPa
2gas reacts 60 minutes at 220 ℃.After reaction finishes, shift out autoclave cooling, open kettle cover, pour out mixed liquor, centrifugal, pour out supernatant liquid, the solid obtaining is bagasse microcrystalline cellulose.To thick product bleach, wash, filter, be dried, pulverization process, obtain lily bagasse microcrystalline cellulose, the degree of polymerization is 108.
Embodiment 6
Accurately take bagasse cellulose pulp 10g, add deionized water 1000g, after fully mixing, soak 60 minutes, pack in autoclave.Pass into CO
2in displacement still, after air, be filled with the CO of 10.0MPa
2gas reacts 10 minutes at 250 ℃.After reaction finishes, shift out autoclave cooling, open kettle cover, pour out mixed liquor, centrifugal, pour out supernatant liquid, the solid obtaining is bagasse microcrystalline cellulose.To thick product bleach, wash, filter, be dried, pulverization process, obtain lily bagasse microcrystalline cellulose, the degree of polymerization is 87.
Embodiment 7
Accurately take bagasse cellulose pulp 10g, add deionized water 800g, after fully mixing, soak 50 minutes, pack in autoclave.Pass into CO
2in displacement still, after air, be filled with the CO of 5.0MPa
2gas reacts 30 minutes at 250 ℃.After reaction finishes, shift out autoclave cooling, open kettle cover, pour out mixed liquor, centrifugal, pour out supernatant liquid, the solid obtaining is bagasse microcrystalline cellulose.To thick product bleach, wash, filter, be dried, pulverization process, obtain lily bagasse microcrystalline cellulose, the degree of polymerization is 51.
Claims (2)
1. a preparation method for microcrystalline cellulose, is characterized in that: be that to take the subcritical water of 140-250 ℃ be reaction media, at CO
2under the catalysis of gas, by degraded sugarcane fiber, usually realize, its processing step is as follows:
(1) raw material is processed: bagasse cellulose pulp is fully mixed with deionized water, soak 10-60 minute, pack in autoclave:
(2) high-temperature high-voltage reaction: pass into CO
2in displacement still, after air, be filled with the CO of 0.5-10MPa
2gas, reaction temperature is 140-250 ℃, the reaction time is 10-180 minute;
(3) product purification: through centrifugation, bleaching, dry, pulverization process, obtain lily bagasse microcrystalline cellulose;
Described bagasse cellulose pulp is the pulp material obtaining from bagasse paper-making pulping;
Described bagasse cellulose pulp and the weight ratio of deionized water are 1: 10-100.
2. the degree of polymerization of the bagasse microcrystalline cellulose that method according to claim 1 obtains is 50-300.
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| CN102392378B true CN102392378B (en) | 2014-04-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12006403B2 (en) | 2018-01-12 | 2024-06-11 | Circ, LLC | Methods for recycling cotton and polyester fibers from waste textiles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114481656B (en) * | 2015-06-11 | 2024-03-22 | 思科有限责任公司 | Method and system for producing pulp, energy and biological derivatives from plant-based and renewable materials |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353310A (en) * | 2000-11-06 | 2002-06-12 | 浙江大学 | Process for preparing cellopolyose reagents series simultaneously |
| CN101362827A (en) * | 2008-09-26 | 2009-02-11 | 复旦大学 | Method for processing cellulose by supercritical carbon dioxide, products and use thereof |
| CN101805807A (en) * | 2010-04-20 | 2010-08-18 | 上海大学 | Method for hydrolyzing cellulose-containing plant waste by taking AlCl3 as catalyst in near-critical water |
| CN101864685A (en) * | 2010-06-21 | 2010-10-20 | 北京工业大学 | Bagasse microcrystalline cellulose and preparation method thereof |
-
2011
- 2011-08-12 CN CN201110230523.1A patent/CN102392378B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353310A (en) * | 2000-11-06 | 2002-06-12 | 浙江大学 | Process for preparing cellopolyose reagents series simultaneously |
| CN101362827A (en) * | 2008-09-26 | 2009-02-11 | 复旦大学 | Method for processing cellulose by supercritical carbon dioxide, products and use thereof |
| CN101805807A (en) * | 2010-04-20 | 2010-08-18 | 上海大学 | Method for hydrolyzing cellulose-containing plant waste by taking AlCl3 as catalyst in near-critical water |
| CN101864685A (en) * | 2010-06-21 | 2010-10-20 | 北京工业大学 | Bagasse microcrystalline cellulose and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12006403B2 (en) | 2018-01-12 | 2024-06-11 | Circ, LLC | Methods for recycling cotton and polyester fibers from waste textiles |
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| CN102392378A (en) | 2012-03-28 |
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