CN104479031A - Method for degrading cellulose by synergic action of mechanical activation and metal salt - Google Patents
Method for degrading cellulose by synergic action of mechanical activation and metal salt Download PDFInfo
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- CN104479031A CN104479031A CN201410787022.7A CN201410787022A CN104479031A CN 104479031 A CN104479031 A CN 104479031A CN 201410787022 A CN201410787022 A CN 201410787022A CN 104479031 A CN104479031 A CN 104479031A
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Abstract
The invention discloses a method for degrading cellulose by synergic action of mechanical activation and a metal salt, belonging to the field of biomass energy and fiber chemicals. The method comprises the following steps: (1) crushing cellulose which serves as a raw material, and screening with a screen of 10-200mesh; (2) mixing the crushed and screened cellulose with a metal salt at a weight ratio of 1:(0.001-0.1) uniformly; and (3) adding the materials mixed uniformly into a mechanical activation reactor, adjusting the mechanical activation temperature to 30-90 DEG C, activating the materials mechanically for 10-180 minutes, and taking the obtained cellulose degradation product out of the mechanical activation reactor. Because the cellulose is degraded by synergic action of mechanical activation and the metal salt, the degree of polymerization of the cellulose can be reduced greatly in a mild condition, the accessibility and the reaction activity of the cellulose degradation product can be improved greatly, and hydrolysis and modification reaction of cellulose can be realized. Little energy is consumed in the whole reaction process, the process for degrading cellulose is simple, the production cycle is short, the cellulose is degraded only under the mechanical force of a ball mill, and the requirement for production equipment is low.
Description
Technical field
The invention belongs to biomass energy and fibre chemistry product field, be specifically related to a kind of method that mechanical activation works in coordination with metal-salt degraded cellulose.
Background technology
Mierocrystalline cellulose is synthesized by photosynthesis primarily of plant, is inexhaustible, the nexhaustible renewable resources of nature.Mierocrystalline cellulose has good biodegradability, biocompatibility, stability and special mechanical property, and has nontoxic, that low price, output are huge feature.In recent years along with the decline of oil, coal reserves and the growth at full speed of oil price, along with growing interest and the attention of various countries' environmental pollution, Mierocrystalline cellulose is considered to the green bio resource of most possible petroleum replacing.From Mierocrystalline cellulose synthesising biological mass-energy source and bio-based chemical, progressively setting up biorefining economic model, and in conjunction with refining of petroleum, realize biorefinery integrated with refining of petroleum, is the effective countermeasure promoting China and even global energy and resource development.In cellulosic conversion process, based on the conversion technology of sugared platform because reaction conditions is gentle, advantages of environment protection gains great popularity.Cellulosic chemical structure is each other with β-1 by D-Glucopyranose ring, the long chain molecule that 4-glycosidic link connects with C1 chair conformation, each glucose basic ring in cellulosic molecule all there are 3 hydroxyls, these hydroxyls in molecule or intermolecular formation hydrogen bond, make Mierocrystalline cellulose be formed the structure of highly crystalline in the mode of coiling at many levels.This complexity and stable Supramolecular morphological structure makes Mierocrystalline cellulose be difficult to be touched by enzyme or other reagent place, causes its reaction efficiency lower, is the principal element of constraints on fiber element biorefining.Want the accessibility of fortifying fibre element, first will destroy cellulosic macromolecular chain structure, increase cellulosic pars amorpha, the contact area of increased fiber element, this is cellulosic pre-treatment namely.Therefore, by carrying out pre-treatment to Mierocrystalline cellulose to destroy cellulosic rock steady structure and to improve cellulosic morphological structure and crystalline texture, increase pars amorpha and specific surface area, improve cellulosic accessibility and reactive behavior and become the crucial research contents that Mierocrystalline cellulose develops.
At present, have the main method that Mierocrystalline cellulose carries out activating pretreatment: (1) Physical.Main employing mechanical disintegration, microwave, ultrasonic wave, high energy electron irradiation etc. process Mierocrystalline cellulose, these methods can make raw material mix loose, hydrogen bond rupture between the Middle molecule of crystallizing field, degree of crystallinity reduces, thus improves cellulosic chemical reactivity or enzymolysis activity; (2) chemical method.Main employing mineral acid, alkali and organic solvent carry out pre-treatment to Mierocrystalline cellulose, make Mierocrystalline cellulose, hemicellulose and xylogen imbibition and destroy its crystallinity, promoting cellulosic dissolving, degraded, improving its accessibility; (3) physical-chemical method.The strong point of main synthesis logos and chemical method, compensates its defect, as steam pre-treatment, pyrolysis pre-treatment with steam quick-fried pre-treatment etc.; (4) biological process.Biological process preconditioning technique utilizes certain micro-organisms to carry out pre-treatment to Mierocrystalline cellulose exactly, reaches the effect improving fibrin reaction activity; (5) combined treatment method.Two or more different pretreatments method main comprehensive, learns from other's strong points to offset one's weaknesses, to reaching desirable pretreating effect.On the whole, above method respectively has superiority, but also has certain limitation, and as mechanical disintegration treatment process is simple, but energy consumption is high; The treatment time such as microwave, ultrasonic wave is short, simple to operate, but cost of equipment is higher, and is difficult to carry out large-scale industrial production; Chemical method is conventional comparatively effective means, but there is the recovery of reagent, neutralization, washing problem, and degradation process loses a considerable amount of Mierocrystalline cellulose.Although organic solvent is easy to reclaim, but there is the restriction of the problems such as corrosion and toxicity, and at substantial industrial chemicals, cause environmental pollution, be difficult to the practical value obtaining large-scale production; The advantage of steam explosion is that energy consumption is low, can interval also can operate continuously, but steam pop operation relates to high voltage equipment, and cost of investment is higher.The treatment capacity of continuous steam explosion comparatively intermittent steam blasting procedure increases to some extent, but device is more complicated, and cost of investment greatly increases; It is low that biological process preconditioning technique has energy consumption, pollution-free, the advantages such as mild condition, but the production cycle that there is again treatment time length and cause is long simultaneously, and thalline can utilize portion of cellulose and hemicellulose, making the deficiencies such as the hydrolysis yield reduction of raw material, thus producing certain distance in addition apart from realizing large industrialized; Combined method can the advantage of comprehensive different pretreatments method, if but be only the superposition of simple effect, not only do not have advantage, and can cause whole too long in flow, processing cost increases.Therefore, find green, economic, simple preconditioning technique and just become pursuing a goal of many investigators.
Metal-salt refers to that metal ion is positively charged ion, and acid ion is a kind of salt of negatively charged ion, is that one can accept electron pair, structure has the material of unoccupied orbital.Common have the inorganic metal salts such as sodium-chlor, zinc chloride, aluminum chloride, ferric sulfate, aluminum nitrate.These metal-salt general industries are produced in a large number, low price.Research shows, metal-salt can effectively destroy cellulosic macromolecular chain structure and crystalline texture, changes cellulosic active surface sum microvoid structure, improves its accessibility and reactive behavior.And metal-salt has green, safely, stablizes, is easy to the advantages such as recovery, can be used as the pretreated attractive reagent of Mierocrystalline cellulose.Current research metal-salt mainly carries out cellulosic effect under aqueous phase system or molten state, there is the problems such as salt concn is high, consumption is large, corrodibility is strong, aftertreatment trouble in aqueous phase system, molten state also also exists the defects such as power consumption is large, temperature is high, poor stability, these all limit the effective application of metal-salt in Mierocrystalline cellulose pre-treatment, a kind of method that can change its using state must be sought, to giving full play to the advantage of metal-salt.
Summary of the invention
A kind of mechanical activation is the object of the present invention is to provide to work in coordination with the method for metal-salt degraded cellulose, can overcome complex process, energy consumption that existing cellulose degradation technology exists high, easily cause environmental pollution, the production cycle long and high deficiency of production process equipment requirements, reach and shorten pretreatment time but the object that effectively can reduce cellulosic degree of polymerization (Degree of Polymerization, DP).
For achieving the above object, present invention employs following technical scheme:
Mechanical activation works in coordination with a method for metal-salt degraded cellulose, comprises the following steps:
(1) cellulosic material is broken, cross 10 ~ 100 mesh sieves;
(2) cellulosic material that is broken, that sieve is mixed for 1:0.001 ~ 0.1 by weight with metal-salt;
(3) material mixed is put into mechanical activation reactor, regulate the mechanical activation temperature of 30 ~ 90 DEG C, after mechanical activation 10 ~ 180min, take out, obtain cellulose degradation product.
Mechanical activation refers to that solid matter is when being subject to the effect of the strong mechanical force such as friction, collision, impact, shearing, make solid while cracking, produce viscous deformation and various types of defect, as lattice distortion, crystal structure degree reduce and even partial amorphism, make some mechanical can be transformed into the interior energy of material, thus improve the reactive behavior of solid.Mechanical activation is an emerging overlapping edges technology, belongs to the category of machinery (power) chemistry.Mechanical activation, at first for the Strengthen education of mineral, is widely used at present in refining of metal, crystal engineering, agricultural, pharmacy industry, refuse process, ultra micro and nano composite material, organic materials synthesis etc.Mechanical force can destroy the high stability ordered structure of natural polymers, and its grain graininess is reduced, and specific surface area increases, degree of crystallinity reduces, molecular rupture, produces a large amount of activity hydroxies with intermolecular hydrogen bond in molecule, and then significantly improves the reactive behavior of polymkeric substance.
Study proof through the present inventor, mechanical activation+metal-salt combination method for pretreating has not been the simple superposition of folk prescription effect to cellulosic effect, but has collaborative coupling.Under the acting in conjunction of mechanical activation and metal-salt, mechanical activation makes Mierocrystalline cellulose while destruction cellulosic structure, the contact condition of metal-salt significantly improves, metal-salt also obviously strengthens cellulosic action effect, therefore in a mild condition just can effective degraded cellulose.In addition, because metal-salt has high thermoconductivity, the local instantaneous high-temperature produced effectively is conducted, promote uniformly transfer heat and the mass transfer of whole system in mechanical force process, improve the efficiency for the treatment of processes, shorten pretreatment time, reduce energy consumption.
Further illustrate as of the present invention, described metal-salt is selected from chemical formula and is
any one compound or the mixture of more than one compounds; Wherein, [M]
x+
for metallic cation, [A]
y–
for acid radical anion;
xor
ybe 1,2,3 or 4.
Further illustrate as of the present invention, described metal-salt preferable alloy chlorate, metal nitrate, metal sulfate, metal perchlorate, metal carbonate.
Preferably, described metal chlorination salt comprises LiCl, AlCl
3, FeCl
3, NaCl, ZnCl
2deng.
Preferably, described metal nitrate comprises Al (NO
3)
3, KNO
3, Fe (NO
3)
3deng.
Preferably, described metal sulfate comprises Al
2(SO
4)
3, Fe
2(SO
4)
3deng.
Preferably, described metal perchlorate comprises KClO
4, Mg (ClO
4)
2deng.
Preferably, described metal carbonate comprises K
2cO
3, Na
2cO
3deng.
Above-mentioned preferred metal-salt realizes commercial scale production all, and the source of goods is wide, low price, has green, safely, stablizes, is easy to the advantages such as recovery.And described metal-salt can be used as the catalyzer that cellulose degradation product is processed into biomass energy or chemical further, being separated without the need to increasing operation, also contributing to improving and producing transformation efficiency.
Further illustrating as foregoing invention, described mechanical activation reactor is the ball mill with constant temperature system.
Cellulosic material moves with abrading-ball in ball mill with metal-salt; the effect of strong mechanical force such as friction, collision, impact, shearing etc. by producing between mill ball and between mill ball and ball grinding cylinder; destroy the wooden protective layer of raw material and change cellulosic crystalline structure; increase cellulosic pars amorpha, thus strengthen metal-salt and cellulosic action effect.The heat that mechanical milling process produces is taken away by constant temperature system, ensures constant temperature ball milling, suppresses the reaction of material generation thermo-sensitivity.Concrete, described constant temperature system is arranged on the coolant circulating system that ball grinding cylinder constant temperature adds cover, and refrigerant is circulating in process and the heat conducting to ball grinding cylinder can taken away, and also by regulating the flow control ball milling temperature of refrigerant, it is very convenient to manipulate.More specifically, described mechanical activation reactor applies for disclosed patent equipment for the applicant: horizontal strengthening polysaccharide modified-high polymer stirring ball-milling reaction device (CN102921512A); A kind of verticle reinforced polysaccharide modified-high polymer stirring ball-milling reaction device (CN102935350A).
Further illustrating as foregoing invention, described cellulosic material derives from the waste after timber, farm crop and their processing.
Mierocrystalline cellulose is the natural high moleculer eompound that standing stock are the abundantest in the world, and raw material sources is in timber, cotton, linters, wheat straw, straw, reed, fiber crops, mulberry skin, paper mulberry skin etc.Wherein, the content of cellulose of cotton, close to 100%, is natural most pure cellulose source.In general timber, Mierocrystalline cellulose accounts for 40 ~ 50%, also has the hemicellulose of 10 ~ 30% and the xylogen of 20 ~ 30%.The Mierocrystalline cellulose average content of grass class stem stalk is about 40%.
Guangxi is located in subtropics, there is very abundant natural fiber resource, produce the plant fiber materials such as a large amount of bagasse, manioc waste, cassava grain stillage, farm crop stem stalk and wood working waste thus, they all contain abundant robust fibre, and content of cellulose is higher.Develop these waste resources, both can prevent the pollution of the environment problem, effectively can improve again utilization ratio and the added value of vegetable fibre.
Compared with prior art, the invention has the beneficial effects as follows:
(1) adopt mechanical activation to work in coordination with metal-salt degraded cellulose, can realize greatly reducing the cellulosic polymerization degree in a mild condition, improve accessibility and the reactive behavior of cellulose degradation product, effectively improve cellulosic utilization ratio and added value.
(2) metal-salt that adopts of the inventive method is cheap, there is green, safely, stablize, be easy to the advantages such as recovery, not easily cause environmental pollution, also can be used as the catalyzer that cellulose degradation product is processed into biomass energy or chemical further, and be separated without the need to increasing operation.
(3) cellulosic material is under the synergy of mechanical activation and metal-salt, can accelerate to destroy cellulosic crystalline structure, and there is the feature of high thermoconductivity due to metal-salt, the local instantaneous high-temperature produced in mechanical force process is effectively conducted, promote uniformly transfer heat and the mass transfer of whole system, improve the efficiency for the treatment of processes, shorten pretreatment time, reduce energy consumption simultaneously.
(4) no matter the inventive method all produces good effect to cellulosic degraded in liquid phase or solid state shape, does not need to carry out dry pre-treatment, effectively reduce operation to moisture raw material.
(5) the inventive method only needs just can be completed by the mechanical force of ball mill under mild conditions (30 ~ 90 DEG C), require low to production unit, and produce without " three wastes ", simple to operate, compared with traditional treatment method, there is the advantages such as low, the pollution-free and equipment investment cost of energy consumption is low, be suitable for large-scale industrial production.
Embodiment
Be described in further detail the present invention below in conjunction with embodiment, the present embodiment is only do clearer explanation to the present invention, instead of limitation of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all drop within protection scope of the present invention.
In embodiment, viscosimetry is adopted to measure the mean polymerisation degree (DP) of cellulosic material used and its degraded product.
Embodiment 1
By the gossypin raw material crushing of DP=1010, cross 10 mesh sieves, then by gossypin raw material 20g good for fragmentation and metal-salt AlCl
30.2g adds in mixing machine, and mixing, then puts into the tumbling ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 50 DEG C after ball milling 30min, and pellet is separated, and obtains the cellulose degradation product of DP=224.
Embodiment 2
By the gossypin raw material crushing of DP=1010, cross 20 mesh sieves, then by gossypin raw material 20g good for fragmentation and metal-salt FeCl
30.12g manually mixes, and then the material mixed is put into the agitating ball mill with constant temperature system, takes out at the mechanical activation temperature of constant temperature 90 DEG C after ball milling 60min, and pellet is separated, and obtains the cellulose degradation product of DP=117.
Embodiment 3
By the gossypin raw material crushing of DP=1010, cross 40 mesh sieves, then by gossypin raw material 20g good for fragmentation and metal-salt Al (NO
3)
30.06g, NaCl0.04g add in mixing machine, mixing, then puts into the tumbling ball mill with constant temperature system by the material mixed, takes out at the mechanical activation temperature of constant temperature 70 DEG C after ball milling 60min, pellet is separated, and obtains the cellulose degradation product of DP=109.
Embodiment 4
By the gossypin raw material crushing of DP=1010, cross 80 mesh sieves, then by gossypin raw material 20g good for fragmentation and metal-salt Fe (NO
3)
30.6g, KNO
30.2g adds in mixing machine, and mixing, then puts into the agitating ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 90 DEG C after ball milling 10min, and pellet is separated, and obtains the cellulose degradation product of DP=102.
Embodiment 5
By the gossypin raw material crushing of DP=2500, cross 60 mesh sieves, then gossypin raw material 20g good for fragmentation and metal-salt LiCl0.3g is added in mixing machine, mixing, then the material mixed is put into the agitating ball mill with constant temperature system, take out after ball milling 120min at the mechanical activation temperature of constant temperature 70 DEG C, pellet is separated, and obtains the cellulose degradation product of DP=136.
Embodiment 6
By the gossypin raw material crushing of DP=2500, cross 80 mesh sieves, then by gossypin raw material 20g good for fragmentation and metal-salt Al (NO
3)
30.2g adds in mixing machine, and mixing, then puts into the tumbling ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 50 DEG C after ball milling 60min, and pellet is separated, and obtains the cellulose degradation product of DP=293.
Embodiment 7
By the Bagasse-cellulose raw material crushing of DP=1300, cross 80 mesh sieves, then by Bagasse-cellulose raw material 20g good for fragmentation and metal-salt Al
2(SO
4)
30.6g adds in mixing machine, and mixing, then puts into the tumbling ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 90 DEG C after ball milling 30min, and pellet is separated, and obtains the cellulose degradation product of DP=227.
Embodiment 8
By the Bagasse-cellulose raw material crushing of DP=1300, cross 80 mesh sieves, then by Bagasse-cellulose raw material 20g and Mg (ClO good for fragmentation
4)
20.7g adds in mixing machine, and mixing, then puts into the agitating ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 30 DEG C after ball milling 90min, and pellet is separated, and obtains the cellulose degradation product of DP=93.
Embodiment 9
The manioc waste cellulosic material of DP=1270 is broken, cross 80 mesh sieves, then by manioc waste cellulosic material 20g good for fragmentation and metal-salt KClO
40.03g, K
2cO
30.07g manually mixes, and then the material mixed is put into the agitating ball mill with constant temperature system, takes out at the mechanical activation temperature of constant temperature 50 DEG C after ball milling 150min, and pellet is separated, and obtains the cellulose degradation product of DP=100.
Embodiment 10
The manioc waste cellulosic material of DP=1270 is broken, cross 80 mesh sieves, then by manioc waste cellulosic material 20g good for fragmentation and metal-salt FeCl
30.25g adds in mixing machine, and mixing, then puts into the tumbling ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 50 DEG C after ball milling 90min, and pellet is separated, and obtains the cellulose degradation product of DP=105.
Embodiment 11
By the corn stalk fiber of DP=1230 element raw material crushing, cross 80 mesh sieves, then by corn stalk fiber good for fragmentation element raw material 20g and metal-salt ZnCl
20.4g, NaCl0.6g add in mixing machine, mixing, then puts into the agitating ball mill with constant temperature system by the material mixed, takes out at the mechanical activation temperature of constant temperature 50 DEG C after ball milling 25min, pellet is separated, and obtains the cellulose degradation product of DP=182.
Embodiment 12
By the corn stalk fiber of DP=1230 element raw material crushing, cross 80 mesh sieves, then by corn stalk fiber good for fragmentation element raw material 20g and metal-salt ZnCl
20.35g adds in mixing machine, and mixing, then puts into the tumbling ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 60 DEG C after ball milling 45min, and pellet is separated, and obtains the cellulose degradation product of DP=176.
Embodiment 13
By the Pine cellulose raw material crushing of DP=1110, cross 60 mesh sieves, then by Pine cellulose raw material 20g good for fragmentation and metal-salt AlCl
30.04g, Na
2cO
30.08g, NaCl0.08g manually mix, and then the material mixed are put into the tumbling ball mill with constant temperature system, take out at the mechanical activation temperature of constant temperature 40 DEG C after ball milling 180min, and pellet is separated, and obtains the cellulose degradation product of DP=92.
Embodiment 14
By the Pine cellulose raw material crushing of DP=1110, cross 80 mesh sieves, then by Pine cellulose raw material 20g good for fragmentation and metal-salt Fe
2(SO
4)
30.9g adds in mixing machine, and mixing, then puts into the agitating ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 80 DEG C after ball milling 45min, and pellet is separated, and obtains the cellulose degradation product of DP=135.
Embodiment 15
By the Pine cellulose raw material crushing of DP=1110, cross 80 mesh sieves, then by Pine cellulose raw material 20g good for fragmentation and metal-salt Fe
2(SO
4)
32.0g adds in mixing machine, and mixing, then puts into the agitating ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 40 DEG C after ball milling 50min, and pellet is separated, and obtains the cellulose degradation product of DP=95.
Embodiment 16
By the Pine cellulose raw material crushing of DP=1110, cross 100 mesh sieves, then by Pine cellulose raw material 20g good for fragmentation and metal-salt Fe
2(SO
4)
30.5g adds in mixing machine, and mixing, then puts into the agitating ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 70 DEG C after ball milling 60min, and pellet is separated, and obtains the cellulose degradation product of DP=123.
Embodiment 17
By the Pine cellulose raw material crushing of DP=1110, cross 100 mesh sieves, then by Pine cellulose raw material 20g good for fragmentation and metal-salt KClO
40.3g adds in mixing machine, and mixing, then puts into the tumbling ball mill with constant temperature system by the material mixed, take out at the mechanical activation temperature of constant temperature 50 DEG C after ball milling 90min, and pellet is separated, and obtains the cellulose degradation product of DP=96.
Claims (10)
1. mechanical activation works in coordination with a method for metal-salt degraded cellulose, it is characterized in that, comprises the following steps:
(1) cellulosic material is broken, cross 10 ~ 100 mesh sieves;
(2) cellulosic material that is broken, that sieve is mixed for 1:0.001 ~ 0.1 by weight with metal-salt;
(3) material mixed is put into mechanical activation reactor, regulate the mechanical activation temperature of 30 ~ 90 DEG C, after mechanical activation 10 ~ 180min, take out, obtain cellulose degradation product.
2. mechanical activation works in coordination with the method for metal-salt degraded cellulose according to claim 1, it is characterized in that, described metal-salt is selected from chemical formula and is
any one compound or the mixture of more than one compounds; Wherein, [M]
x+
for metallic cation, [A]
y–
for acid radical anion;
xor
ybe 1,2,3 or 4.
3. mechanical activation works in coordination with the method for metal-salt degraded cellulose according to claim 2, it is characterized in that, described metal-salt is metal chlorination salt, metal nitrate, metal sulfate, metal perchlorate, metal carbonate.
4. mechanical activation works in coordination with the method for metal-salt degraded cellulose according to claim 3, it is characterized in that, described metal chlorination salt comprises LiCl, AlCl
3, FeCl
3, NaCl, ZnCl
2.
5. mechanical activation works in coordination with the method for metal-salt degraded cellulose according to claim 3, it is characterized in that, described metal nitrate comprises Al (NO
3)
3, KNO
3, Fe (NO
3)
3.
6. mechanical activation works in coordination with the method for metal-salt degraded cellulose according to claim 3, it is characterized in that, described metal sulfate comprises Al
2(SO
4)
3, Fe
2(SO
4)
3.
7. mechanical activation works in coordination with the method for metal-salt degraded cellulose according to claim 3, it is characterized in that, described metal perchlorate comprises KClO
4, Mg (ClO
4)
2.
8. mechanical activation works in coordination with the method for metal-salt degraded cellulose according to claim 3, it is characterized in that, described metal carbonate comprises K
2cO
3, Na
2cO
3.
9. work in coordination with the method for metal-salt degraded cellulose according to the arbitrary described mechanical activation of claim 1 ~ 8, it is characterized in that, described mechanical activation reactor is the ball mill with constant temperature system.
10. mechanical activation works in coordination with the method for metal-salt degraded cellulose according to claim 9, it is characterized in that, described cellulosic material derives from the waste after timber, farm crop and their processing.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543308A (en) * | 2015-12-17 | 2016-05-04 | 广西大学 | Mechanical activation-metal salt reinforcement-combined starchy raw material saccharification method |
| WO2017074270A3 (en) * | 2015-10-29 | 2017-07-20 | Scg Packaging Public Company Limited | Construction materials comprising modified celluloses |
| CN107233916A (en) * | 2017-06-27 | 2017-10-10 | 广西大学 | Carry the preparation method and applications of the cellulose ester-based spheric catalyst of hophornbeam matter |
| CN109706273A (en) * | 2017-10-26 | 2019-05-03 | 中国科学院大连化学物理研究所 | A kind of method of phosphorus pentoxide catalysis lignocellulosic hydrolysed ferment |
-
2014
- 2014-12-18 CN CN201410787022.7A patent/CN104479031A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017074270A3 (en) * | 2015-10-29 | 2017-07-20 | Scg Packaging Public Company Limited | Construction materials comprising modified celluloses |
| CN108495828A (en) * | 2015-10-29 | 2018-09-04 | Scg包装有限公司 | Construction material including modified cellulose |
| CN105543308A (en) * | 2015-12-17 | 2016-05-04 | 广西大学 | Mechanical activation-metal salt reinforcement-combined starchy raw material saccharification method |
| CN107233916A (en) * | 2017-06-27 | 2017-10-10 | 广西大学 | Carry the preparation method and applications of the cellulose ester-based spheric catalyst of hophornbeam matter |
| CN107233916B (en) * | 2017-06-27 | 2019-10-01 | 广西大学 | Carry the preparation method and applications of the cellulose ester-based spheric catalyst of hophornbeam matter |
| CN109706273A (en) * | 2017-10-26 | 2019-05-03 | 中国科学院大连化学物理研究所 | A kind of method of phosphorus pentoxide catalysis lignocellulosic hydrolysed ferment |
| CN109706273B (en) * | 2017-10-26 | 2022-09-16 | 中国科学院大连化学物理研究所 | Method for catalyzing hydrolysis fermentation of lignocellulose by phosphorus pentoxide |
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Application publication date: 20150401 |