CN114276975A - Preparation method of hollow and multi-hollow hybrid cells - Google Patents
Preparation method of hollow and multi-hollow hybrid cells Download PDFInfo
- Publication number
- CN114276975A CN114276975A CN202110354860.5A CN202110354860A CN114276975A CN 114276975 A CN114276975 A CN 114276975A CN 202110354860 A CN202110354860 A CN 202110354860A CN 114276975 A CN114276975 A CN 114276975A
- Authority
- CN
- China
- Prior art keywords
- raw material
- bamboo
- hollow
- bleaching
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 210000004754 hybrid cell Anatomy 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 115
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 115
- 241001330002 Bambuseae Species 0.000 claims abstract description 115
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 115
- 239000011425 bamboo Substances 0.000 claims abstract description 115
- 239000002994 raw material Substances 0.000 claims abstract description 94
- 229920005610 lignin Polymers 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000004061 bleaching Methods 0.000 claims abstract description 29
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 238000007710 freezing Methods 0.000 claims abstract description 20
- 230000008014 freezing Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000010902 straw Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 6
- 241000609240 Ambelania acida Species 0.000 claims abstract description 5
- 235000014676 Phragmites communis Nutrition 0.000 claims abstract description 5
- 241000209140 Triticum Species 0.000 claims abstract description 5
- 235000021307 Triticum Nutrition 0.000 claims abstract description 5
- 239000010905 bagasse Substances 0.000 claims abstract description 5
- 238000010411 cooking Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 26
- 239000007800 oxidant agent Substances 0.000 claims description 24
- 229920002678 cellulose Polymers 0.000 claims description 23
- 239000001913 cellulose Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- 108090000790 Enzymes Proteins 0.000 claims description 22
- 102000004190 Enzymes Human genes 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 238000004108 freeze drying Methods 0.000 claims description 20
- 230000001590 oxidative effect Effects 0.000 claims description 19
- 239000012670 alkaline solution Substances 0.000 claims description 18
- 244000302661 Phyllostachys pubescens Species 0.000 claims description 15
- 235000003570 Phyllostachys pubescens Nutrition 0.000 claims description 15
- 238000004073 vulcanization Methods 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000002255 enzymatic effect Effects 0.000 claims description 8
- 239000012595 freezing medium Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010257 thawing Methods 0.000 claims description 7
- 239000004155 Chlorine dioxide Substances 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 claims description 5
- 108010029541 Laccase Proteins 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000009896 oxidative bleaching Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 108010059896 Manganese peroxidase Proteins 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 3
- 150000004967 organic peroxy acids Chemical class 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229940045872 sodium percarbonate Drugs 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 238000000352 supercritical drying Methods 0.000 claims description 3
- 235000005731 Bambusa membranacea Nutrition 0.000 claims description 2
- 240000007880 Phyllostachys bambusoides Species 0.000 claims 1
- 235000001550 Phyllostachys bambusoides Nutrition 0.000 claims 1
- 241000544428 Phyllostachys glauca Species 0.000 claims 1
- 240000005827 Phyllostachys nigra Species 0.000 claims 1
- 235000010717 Phyllostachys nigra Nutrition 0.000 claims 1
- 240000009132 Sagittaria sagittifolia Species 0.000 claims 1
- 235000006466 Sagittaria sagittifolia Nutrition 0.000 claims 1
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 claims 1
- 210000004027 cell Anatomy 0.000 abstract description 42
- 239000000835 fiber Substances 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 241000196324 Embryophyta Species 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 description 14
- 239000011734 sodium Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 230000002792 vascular Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 238000003701 mechanical milling Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000010804 Maranta arundinacea Nutrition 0.000 description 1
- 244000145580 Thalia geniculata Species 0.000 description 1
- 235000012419 Thalia geniculata Nutrition 0.000 description 1
- -1 and simultaneously Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 210000004738 parenchymal cell Anatomy 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Landscapes
- Paper (AREA)
Abstract
The invention relates to a preparation method of hollow and multi-hollow hybrid cells, which comprises the following steps: (1) the method comprises the following steps of (1) taking bamboo, reed, straw, wheat straw, bagasse and processing residues thereof as raw materials, and carrying out alkali cooking and bleaching to remove lignin and hemicellulose to obtain a delignified raw material; (2) freezing and unfreezing the delignified raw material to obtain a wet raw material, drying the wet raw material until the water content is less than or equal to 10%, and separating to obtain hollow and porous hybrid cells. The invention uses the raw material rich in parenchyma cells to prepare hollow and porous hybrid cells, the yield can reach 12 percent, the purity can reach more than 99 percent, and the invention basically has no impurities such as short fibers and the like, and can realize the multi-component full utilization of plants; the prepared hybrid cells have hollow and porous structures, pores are distributed in the range of 1-50nm, and the specific surface area is 10-150 m2/g。
Description
Technical Field
The invention relates to the field of thin-wall cell utilization, in particular to a method for preparing hollow and multi-hollow hybrid cells by using thin-wall cells.
Background
The non-wood pulp raw materials such as bamboo, reed, straw, wheat straw, bagasse and the like are industrially utilized in the industries of artificial board manufacturing, paper pulp manufacturing, bamboo fiber processing, bamboo charcoal processing and the like, but a mature method for separating parenchyma cells from vascular bundle tissues does not exist. The cell wall of the parenchyma cell is of a multilayer structure, a large number of pores (the diameter is about 1 mu m) are distributed on the surface, the parenchyma cell mainly takes a long cell, the length of the parenchyma cell is 50-100 mu m, the width of the parenchyma cell is 40-50 mu m, and the parenchyma cell has the main function of storing nutrients. Although the parenchyma cell content of many plants is 20-60%, cellulose content is low relative to other fiber cell content, so that the cellulose is basically discarded as "interfering" substance in pulp and paper making or cellulose products, and the cellulose is mostly discharged to the outside of a production system in the form of waste or wastewater in the production process, thereby causing resource waste.
At present, researchers have paid attention to the waste of parenchyma cells in the pulping and papermaking process of non-wood pulp raw materials, and the parenchyma cells obtained by separation through a plurality of different methods mainly comprise the following two types:
(1) in 2015 Wang et al ground bamboo into small particles, screened to remove parenchyma cells, and purified to obtain parenchyma cells after removing lignin and cellulose (Industrial Crops and Products,2015,71, 80-88).
(2) Zhang et al ground moso bamboo into powder in 2020, sieved with 30 mesh and 60 mesh sieves, soaked in deionized water for 2 minutes, collected parenchyma cells floating on the water surface by the difference in density, air dried, and purified to obtain parenchyma cells (Materials,2020,13, 237).
The method needs to crush bamboo into small particles, so that a large number of parenchyma cells are broken, the yield is low, a large number of short fibers are doped in a sample due to the similar density of the parenchyma cells and the fiber cells, and meanwhile, the preparation process is long and complex, so that the parenchyma cells are seriously shrunken.
Disclosure of Invention
The invention aims to provide a method for preparing hollow and multi-hollow hybrid cells by using parenchyma cells aiming at the problem of the ineffective resource utilization of parenchyma cell components and developing new application of the parenchyma cells.
In order to achieve the above object, the present invention adopts the following technical solutions.
A method for preparing hollow and multi-hollow hybrid cells comprises the following steps:
(1) the raw material is subjected to alkaline boiling and bleaching to remove lignin and hemicellulose to obtain a delignified raw material;
(2) freezing and unfreezing the delignified raw material to obtain a wet raw material, drying the wet raw material until the water content is less than or equal to 10%, and separating to obtain hollow and porous hybrid cells;
the raw materials are one or more of bamboo, reed, straw, wheat straw and bagasse.
Preferably, the bamboo material is one or more of moso bamboo, arrowhead bamboo, white sandwich bamboo, stay green bamboo, pink bamboo, green bamboo, bamboo processing residues and pulp and paper making residues.
Preferably, the lignin content of the alkaline-cooked raw material is less than or equal to 30 wt%; further preferably, the lignin content of the delignification raw material is 5-25 wt%; more preferably, the delignification raw material has a lignin content of 5% to 25%; the content of hemicellulose is 8-17%; the cellulose content is 65-79%;
preferably, the alkaline cooking treatment comprises: the raw materials are put into alkaline solution, and the heating temperature is 70-160 ℃.
Preferably, the alkali amount of the alkaline solution is 5-30 wt%, and the vulcanization degree is 15-30 wt%.
Preferably, the alkaline solution comprises at least one of sodium hydroxide, potassium hydroxide, sodium sulfite, sodium sulfide, sodium carbonate, sodium sulfate, and sodium thiosulfate; more preferably, the alkaline solution comprises sodium hydroxide and at least one of sodium sulfite and sodium sulfide.
Preferably, the solid-to-liquid ratio of the raw material to the alkaline solution is 1: 4-1: 20, and more preferably, the solid-to-liquid ratio of the raw material to the alkaline solution is 1: 4-1: 10. .
Preferably, the delignified feedstock has a lignin content of 25 wt% or less; further preferably, the lignin content of the delignification raw material is 1-16 wt%; more preferably, the delignification raw material lignin content is 1% to 16%; the content of hemicellulose is 8-15%; the cellulose content is 73-92%;
preferably, the bleaching treatment comprises an oxidative bleaching treatment and/or an enzymatic bleaching treatment.
Preferably, the oxidative bleaching treatment comprises: placing the alkali-boiled raw material in an oxidant solution, heating at 60-120 ℃, and washing the raw material subjected to oxidation bleaching treatment to be neutral by water.
Preferably, the amount of the oxidant is 0.2-5 wt% of the raw materials, and the solid-to-liquid ratio is 1: 4-1: 10.
Preferably, in the oxidizing agent solution, the oxidizing agent is at least one of hydrogen peroxide, hypohalous acid or a salt thereof, organic peroxy acid, sodium percarbonate, chlorine dioxide, oxygen, ozone, borohydride, and dithionite; preferably, the oxidizing agent is any one of hydrogen peroxide, oxygen, ozone and chlorine dioxide.
More preferably, in the oxidant solution, the mass content of the oxidant is 0.2-5 wt%; further preferably, the oxidant solution further comprises 0.1-2.5 wt% of sodium hydroxide.
Preferably, the enzymatic bleaching treatment comprises: enzyme bleaching is carried out on the raw material after alkaline boiling, the dosage of the enzyme is 0.2-2 wt% of the raw material, the temperature is 55-75 ℃, and the pH is 4.0-6.
Preferably, the solid-to-liquid ratio of the enzyme bleaching treatment is 1: 4-1: 10.
Preferably, the enzyme used in the enzymatic bleaching process comprises one or more of xylanase, manganese peroxidase, laccase; more preferably a xylanase and laccase in combination.
Preferably, the freezing temperature of the delignified raw material is-30 to 0 ℃, and the thawing temperature of the delignified raw material is 20 to 100 ℃.
Preferably, the wet raw material is dried by any one of freeze drying, supercritical drying, vacuum oven drying and forced air drying.
Preferably, the freeze drying further comprises a freezing medium, wherein the freezing medium is one or more of water, ethanol, tert-butyl alcohol and acetone in any combination.
The preparation method of the porous hollow fiber micro polyhedron provided by the invention develops new application of bamboo wood thin-wall cells, further realizes multi-component full utilization of bamboo wood, and avoids waste of bamboo wood resources.
The preparation method of the hollow and porous hybrid cell provided by the invention takes the parenchyma cell as a raw material to prepare the hollow and porous hybrid cell, the yield (the mass percentage of the parenchyma cell to the unprocessed bamboo chips) reaches 12 percent, the purity is more than 99 percent, and the hollow and porous hybrid cell is basically free of impurities such as short fibers and the like.
According to the preparation method of the hollow and porous hybrid cell, the hybrid cell prepared has a hollow and porous structure, pores are distributed at 1-50nm, and the specific surface area is 10-150 m2The hybrid cells can be used for preparing chromatographic column fillers, catalyst carriers, bamboo carbon materials with high adsorption capacity, pesticide slow release, drug slow release, biomedical materials, sewage treatment and the like.
Drawings
FIG. 1 is a scanning electron micrograph of hollow, porous hybrid cells;
FIG. 2 is a scanning electron micrograph of a hybrid cell prepared by physically separating parenchymal cells;
FIG. 3 is a graph showing the adsorption-desorption curves of hollow and porous hetero-cells in example 4.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of hollow and porous hybrid cells, which comprises the following steps:
(1) the raw material is subjected to alkaline boiling and bleaching to remove lignin and hemicellulose to obtain a delignified raw material;
(2) freezing and unfreezing the delignified raw material to obtain a soft wet raw material, drying the wet raw material until the water content is less than or equal to 10%, and separating to obtain hollow and porous hybrid cells.
According to the invention, the lignin content of the alkaline-cooked raw material is preferably less than or equal to 30 wt%; preferably, the lignin content of the delignification raw material is 5-25 wt%; more preferably, the delignification raw material has a lignin content of 5% to 25%; the content of hemicellulose is 8-17%; the cellulose content is 65-79%; the thin-wall cells and vascular bundle tissues of the delignified raw material are easy to separate in the freezing-thawing thin process.
According to the invention, the raw material is a raw material with high parenchyma cell content, preferably, the raw material is one or more of bamboo, reed, straw, wheat straw and bagasse; more preferably, the raw material is one or more of moso bamboo, arrowroot bamboo, white bamboo, stay green bamboo, pink bamboo, green bamboo, bamboo processing residues and pulp and paper making residues, and the raw material has high parenchyma cell content but cannot be effectively utilized at present.
According to the invention, the content of hemicellulose and lignin in the bamboo raw material is regulated and controlled to be less than or equal to 30 wt% by controlling the alkaline cooking condition, so that parenchyma cells and vascular bundle tissues are easily separated, and the hollow and porous structure of hybrid cells is completely maintained.
According to the invention, the lignin and hemicellulose in the raw material can be quickly dissolved by alkaline boiling in hot alkaline liquor, and the content of the lignin and hemicellulose in the raw material is controlled by conditions such as reaction temperature, reaction time, alkaline liquor concentration and the like; preferably, the alkali treatment comprises: the raw material is put into alkaline solution and heated to 70-160 ℃ for 1-12 hours.
According to the invention, preferably, the alkali amount of the alkaline solution is 5-30 wt%, and the vulcanization degree is 15-30 wt%; the alkaline solution can effectively control the content of lignin and hemicellulose in the raw material, and simultaneously, cellulose in the raw material is not easy to damage.
According to the present invention, preferably, the alkaline solution contains at least one of sodium hydroxide, potassium hydroxide, sodium sulfite, sodium sulfide, sodium carbonate, sodium sulfate, and sodium thiosulfate; more preferably, the alkaline solution comprises sodium hydroxide and at least one of sodium sulfite and sodium sulfide; by adopting the preferable alkaline solution, the content of lignin and hemicellulose in the raw material can be effectively controlled, and simultaneously, cellulose in the raw material is not easy to damage.
According to the invention, the solid-to-liquid ratio of the raw material to the alkaline solution is 1: 4-1: 20, and more preferably, the solid-to-liquid ratio of the raw material to the alkaline solution is 1: 4-1: 10; within the range of the solid-to-liquid ratio, the content of lignin and hemicellulose in the raw material can be controlled.
According to the invention, the lignin content of the delignified feedstock is less than or equal to 25 wt%; preferably, the lignin content of the delignification raw material is 1-16 wt%; more preferably, the delignification raw material lignin content is 1% to 16%; the content of hemicellulose is 6-15%; the cellulose content is 73-92%; the thin-wall cells and vascular bundle tissues of the delignified raw material are easy to separate in the freezing-thawing thin process.
According to the invention, the oxidative bleaching treatment comprises: washing the alkali-boiled raw material to be neutral, placing the raw material in an oxidant solution, heating the raw material at 60-120 ℃ for 1-5 hours, and washing the raw material subjected to oxidation bleaching treatment to be neutral by water; by adopting the oxidation bleaching conditions, the contents of lignin and hemicellulose in the raw materials can be effectively controlled.
According to the invention, preferably, in the oxidant solution, the mass content of the oxidant is 0.2-5 wt%, and the solid-to-liquid ratio is 1: 4-1: 10.
According to the present invention, the oxidizing agent is an oxidizing agent conventional in the art, and comprises at least one of hydrogen peroxide, hypohalous acid or salt thereof, organic peroxy acid, sodium percarbonate, chlorine dioxide, oxygen, ozone, borohydride, and dithionite; preferably any one of hydrogen peroxide, oxygen, ozone and chlorine dioxide; the bleaching treatment by adopting the oxidant is green and pollution-free.
According to the invention, preferably, the mass content of the oxidant in the oxidant solution is 0.2-5 wt%, and further preferably, the oxidant solution further contains 0.1-2.5 wt% of sodium hydroxide.
According to the present invention, preferably, the enzymatic bleaching treatment comprises: the alkaline boiled raw material is enzyme bleached, the enzyme dosage is 0.2-2 wt% of the raw material, the temperature is 55-75 ℃, and the pH is 4.0-6.
According to the invention, the solid-to-liquid ratio of the enzyme bleaching treatment is preferably 1: 4-1: 10.
According to the present invention, preferably, the enzyme used in the enzymatic bleaching process comprises one or more of xylanase, manganese peroxidase, laccase; more preferably a xylanase and laccase in combination.
The reaction conditions in the freezing and thawing process are not particularly limited as long as the acting force between the parenchyma cells and the fiber bundles in the raw materials can be destroyed; preferably, the freezing temperature of the delignification raw material is-30 to 0 ℃, and the freezing time is 1 to 24 hours; the thawing temperature of the delignified raw material is 20-100 ℃; the adoption of the freezing-thawing condition can make the wet bamboo chips looser, because the volume of water expands when forming ice, the distances between the parenchyma cells and the fiber bundles are increased, the interaction force between the parenchyma cells and the fiber bundles is damaged, and the parenchyma cells are separated.
According to the present invention, the wet raw material drying method is a drying method that is conventional in the art, and as long as water in the wet raw material can be removed, it is preferable that the drying method is any one of freeze drying, supercritical drying, vacuum oven drying, and forced air drying; more preferably, the drying method is freeze drying, and the original polyhedral structure of the parenchyma cell can be completely maintained by adopting the freeze drying.
According to the invention, the step (3) of freeze-drying further comprises placing the wet raw material in a freezing medium, preferably, the freezing medium is one or more of water, ethanol, tert-butyl alcohol and acetone in any combination; more preferably t-butanol, the preferred freezing medium has a higher freezing point and a higher saturated vapor pressure, and the use of the preferred refrigerant is advantageous in saving freeze-drying time.
The present invention will be further described with reference to the following embodiments, examples, comparative examples and test results, wherein the yield is the ratio of the mass of the prepared polyhedron to the mass of the untreated bamboo chips, and the content of the foreign cells of the untreated bamboo chips used in the present experiment is about 20%.
Example 1
(1) Moso bamboo pieces (bamboo 1cm thick, cut into 10cm long and 1cm wide);
(2) placing bamboo chips in NaOH and Na2Heating S mixed solution (alkali amount of 20%, vulcanization degree of 25%, solid-to-liquid ratio of 1:4) at 150 deg.C for 2 hr, washing with water to neutrality, and placing bamboo chips in 4 wt% H2O2Heating the bamboo chips and 1 wt% of NaOH solution at 70 ℃ for 2h, and washing the bamboo chips with water to be neutral to obtain delignified bamboo chips;
(3) and (3) putting the delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, then unfreezing at 25 ℃ to obtain wet bamboo chips, putting the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12 h. Finally, monodisperse, homogeneous hybrid cells were obtained by mechanical milling with a yield of 10.1%, a cellulose content of 86%, a hemicellulose content of 8% and a lignin content of 6%.
Example 2
(1) Moso bamboo pieces (bamboo 1cm thick, cut into 10cm long and 1cm wide);
(2) placing bamboo chips in NaOH and Na2Heating S (alkali content of 20%, vulcanization degree of 25%, solid-to-liquid ratio of 1:4) at 150 deg.C for 3 hr, washing with water to neutrality, and placing bamboo pieces in 4 wt% H2O2Heating the bamboo chips and 1 wt% of NaOH solution at 70 ℃ for 2h, and washing the bamboo chips with water to be neutral to obtain delignified bamboo chips;
(3) and (3) putting the delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, then unfreezing at 25 ℃ to obtain wet bamboo chips, putting the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12 h. Finally, monodisperse, homogeneous hybrid cells were obtained by mechanical extrusion with a yield of 9.6%, a cellulose content of 89%, a hemicellulose content of 7% and a lignin content of 4%.
Example 3
(1) Moso bamboo pieces (bamboo 1cm thick, cut into 10cm long and 1cm wide);
(2) placing bamboo chips in NaOH and Na2Heating S (alkali content 15%, vulcanization degree 25%, solid-to-liquid ratio 1:4) at 150 deg.C for 2 hr, washing with water to neutrality, and placing bamboo sheet in 4 wt% H2O2Heating the bamboo chips and 1 wt% of NaOH solution at 70 ℃ for 2h, and washing the bamboo chips with water to be neutral to obtain delignified bamboo chips;
(3) and (3) putting the delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, then unfreezing at 25 ℃ to obtain wet bamboo chips, putting the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12 h. Finally, monodisperse, homogeneous hybrid cells were obtained by mechanical extrusion with a yield of 10.3%, a cellulose content of 83%, a hemicellulose content of 7% and a lignin content of 10%.
Example 4
(1) Moso bamboo pieces (bamboo 1cm thick, cut into 10cm long and 1cm wide);
(2) placing bamboo chips in NaOH and Na2Heating S (alkali content 15%, vulcanization degree 20%, solid-to-liquid ratio 1:4) at 150 deg.C for 2 hr, washing with water to neutrality, and placing bamboo pieces in 4 wt% H2O2Heating the bamboo chips and 1 wt% of NaOH solution at 70 ℃ for 2h, and washing the bamboo chips with water to be neutral to obtain delignified bamboo chips;
(3) and (3) putting the delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, then unfreezing at 25 ℃ to obtain wet bamboo chips, putting the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12 h. Finally, monodisperse, homogeneous hybrid cells were obtained by mechanical extrusion with a yield of 10.5%, a cellulose content of 79%, a hemicellulose content of 8% and a lignin content of 13%.
Example 5
(1) Moso bamboo pieces (bamboo 1cm thick, cut into 10cm long and 1cm wide);
(2) placing bamboo chips in NaOH and Na2Heating at 160 deg.C for 2H in S (alkali content 25%, vulcanization degree 25%, solid-to-liquid ratio 1:4), washing with water to neutrality, and placing bamboo sheet in 4 wt% H2O2Heating the bamboo chips and 1 wt% of NaOH solution at 70 ℃ for 2h, and washing the bamboo chips with water to be neutral to obtain delignified bamboo chips;
(3) and (3) putting the delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, then unfreezing at 25 ℃ to obtain wet bamboo chips, putting the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12 h. Finally, monodisperse, homogeneous hybrid cells were obtained by mechanical extrusion with a yield of 9.5%, a cellulose content of 88%, a hemicellulose content of 6% and a lignin content of 6%.
Example 6
(1) Moso bamboo pieces (bamboo 1cm thick, cut into 10cm long and 1cm wide);
placing bamboo chips in NaOH and Na2Pre-soaking the S mixed solution (the alkali content is 20%, the vulcanization degree is 25%, and the solid-to-liquid ratio is 1:4) for 12h, heating at 150 ℃ for 2h, and washing with water to be neutral after the reaction is finished;
(2) carrying out enzyme bleaching on the alkali-treated raw material, wherein the enzyme dosage is 1.8 wt%, the temperature is 55 ℃, the pH is 4.7, the time is 2.0 hours, and the solid-to-liquid ratio is 1: 10;
(3) placing delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, unfreezing at 25 ℃ to obtain wet bamboo chips, placing the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12 h. Monodisperse, homogeneous hybrid cells were obtained by mechanical rubbing with a yield of 12.0%, cellulose of 86%, hemicellulose of 10% and lignin of 4%.
Example 7
(1) Moso bamboo pieces (bamboo 1cm thick, cut into 10cm long and 1cm wide);
placing bamboo chips in NaOH and Na2Pre-soaking the S mixed solution (the alkali content is 20%, the vulcanization degree is 25%, and the solid-to-liquid ratio is 1:4) for 12h, heating at 150 ℃ for 2h, and washing with water to be neutral after the reaction is finished;
(2) carrying out enzyme bleaching on the alkali-treated raw material, wherein the enzyme dosage is 1.8 wt%, the temperature is 55 ℃, the pH is 4.7, the time is 2.0 hours, and the solid-to-liquid ratio is 1: 10;
(3) placing delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, unfreezing at 25 ℃ to obtain wet bamboo chips, placing the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12 h. Monodisperse, homogeneous hybrid cells were obtained by mechanical rubbing with a yield of 12.0%, cellulose of 86%, hemicellulose of 10% and lignin of 4%.
Example 8
(1) Moso bamboo pieces (bamboo 1cm thick, cut into 10cm long and 1cm wide);
placing bamboo chips in NaOH and Na2Pre-soaking the S mixed solution (the alkali content is 20%, the vulcanization degree is 25%, and the solid-to-liquid ratio is 1:4) for 12h, heating at 150 ℃ for 2h, and washing with water to be neutral after the reaction is finished;
(2) carrying out enzyme bleaching on the alkali-treated raw material, wherein the enzyme dosage is 1.8 wt%, the temperature is 55 ℃, the pH is 3.7, the time is 2.0 hours, and the solid-to-liquid ratio is 1: 10;
(3) placing delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, unfreezing at 25 ℃ to obtain wet bamboo chips, placing the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12 h. Monodisperse, homogeneous hybrid cells were obtained by mechanical rubbing with a yield of 10.3%, 88% cellulose, 9.2% hemicellulose and 2.8% lignin.
Example 9
(1) Moso bamboo pieces (bamboo 1cm thick, cut into 10cm long and 1cm wide);
placing bamboo chips in NaOH and Na2Pre-soaking the S mixed solution (the alkali content is 20%, the vulcanization degree is 25%, and the solid-to-liquid ratio is 1:4) for 12h, heating at 150 ℃ for 2h, and washing with water to be neutral after the reaction is finished;
(2) carrying out enzyme bleaching on the alkali-treated raw material, wherein the enzyme dosage is 1.8 wt%, the temperature is 55 ℃, the pH is 6.2, the time is 2.0 hours, and the solid-to-liquid ratio is 1: 10;
(3) placing delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, unfreezing at 25 ℃ to obtain wet bamboo chips, placing the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12 h. Monodisperse, homogeneous hybrid cells were obtained by mechanical rubbing with a yield of 9.7%, cellulose of 88.4%, hemicellulose of 8.9% and lignin of 2.7%.
Comparative example 1
Drying bamboo chips at 105 deg.C for 4h, pulverizing into powder, and sieving with 100 mesh standard sieve to obtain heterocyte aggregate with heavily damaged cell structure and doped with a large amount of aggregated short fiber bundles.
Comparative example 2
(1) Moso bamboo powder (100 mesh);
(2) placing bamboo powder in NaOH and Na2Heating S mixed solution (alkali amount of 20%, vulcanization degree of 25%, solid-to-liquid ratio of 1:4) at 150 deg.C for 2 hr, washing with water to neutrality, and placing bamboo chips in 4 wt% H2O2Heating the bamboo powder and 1 wt% NaOH solution at 70 ℃ for 2h, and washing the bamboo powder with water to be neutral to obtain delignified bamboo powder;
(3) and (3) putting the delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, then unfreezing at 25 ℃ to obtain wet bamboo chips, putting the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12 h. Finally, monodisperse, homogeneous hybrid cells were obtained by mechanical milling with a yield of 8.6%, a cellulose content of 87%, a hemicellulose content of 8% and a lignin content of 5%. (ii) a
The mixed cells and the short fibers are mixed together and cannot be separated, the structure of the mixed cells is incomplete, and the cell structure is seriously damaged due to the crushing treatment.
Comparative example 3
(1) Moso bamboo pieces (bamboo 1cm thick, cut into 10cm long and 1cm wide);
(2) placing bamboo chips in NaOH and Na2Heating S mixed solution (alkali amount of 20%, vulcanization degree of 25%, solid-to-liquid ratio of 1:4) at 150 deg.C for 2 hr, washing with water to neutrality, and placing bamboo chips in 4 wt% H2O2Heating the bamboo chips and 1 wt% of NaOH solution at 70 ℃ for 2h, and washing the bamboo chips with water to be neutral to obtain delignified bamboo chips;
(3) and (3) placing the delignified bamboo chips in tert-butyl alcohol for replacing for 12h, and then carrying out freeze drying for 12 h. Finally, the hybrid cells were obtained by mechanical milling with a yield of 7.3%, a cellulose content of 84%, a hemicellulose content of 8% and a lignin content of 8%.
Most of the heterocells are firmly adhered to the bamboo fibers and are difficult to separate, and most of the obtained heterocells are shriveled and seriously damaged.
The yield of the hollow and porous hybrid cell prepared by the embodiment of the invention can reach 12.0 percent, wherein,
FIG. 1 is a scanning electron microscope picture of hollow and porous hybrid cells prepared by the preparation method of the invention, and it can be seen that the hybrid cells prepared by the invention are perfect in appearance, full, high in purity up to more than 99%, and basically free of short fibers and other impurities.
As can be seen from FIG. 2, the physical method for separating the heterocyte has a shriveled and uneven appearance and more short fibers.
FIG. 3 is the adsorption-desorption curve of the hollow and porous hetero-cells of example 4, the adsorption-desorption curve has a hysteresis loop and the pores are distributed in 1-50nm, and the specific surface area is 10-150 m2And g, indicating that the heterocell has a hierarchical pore structure.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the individual specific technical features in any suitable way. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (10)
1. A method for preparing hollow and multi-hollow hybrid cells is characterized by comprising the following steps:
(1) the raw material is subjected to alkaline boiling and bleaching to remove lignin and hemicellulose to obtain a delignified raw material;
(2) freezing and unfreezing the delignified raw material to obtain a wet raw material, drying the wet raw material until the water content is less than or equal to 10%, and separating to obtain hollow and porous hybrid cells;
the raw materials are one or more of bamboo, reed, straw, wheat straw and bagasse.
2. The preparation method of claim 1, wherein the bamboo material is one or more of moso bamboo, Sagittaria sagittifolia, white bamboo, Phyllostachys bambusoides, Phyllostachys glauca, Phyllostachys nigra, bamboo material processing residues and pulp and paper making residues.
3. The production method according to claim 1 or 2,
the lignin content of the delignification raw material is less than or equal to 30 wt%; preferably, the lignin content of the delignification raw material is 1-16 wt%; more preferably, the delignification raw material lignin content is 1% to 16%; the content of hemicellulose is 6-15%; the cellulose content is 73-92%; and/or
The alkaline cooking treatment comprises the following steps: putting the raw materials into an alkaline solution, and heating at 70-160 ℃;
the bleaching treatment comprises oxidative bleaching and/or enzymatic bleaching;
the oxidative bleaching comprises: washing the alkali-boiled raw material to neutrality, placing the raw material in an oxidant solution, heating the raw material at 60-120 ℃, and washing the raw material subjected to oxidation bleaching to neutrality by using water;
the enzymatic bleaching comprises: enzyme bleaching is carried out on the raw material after alkaline cooking, wherein the dosage of enzyme bleaching enzyme is 0.2-2 wt% of the raw material, the pH is 4.0-6, and the temperature is 55-75 ℃.
4. The production method according to any one of claims 1 to 3, wherein the alkali solution is used in an amount of 5 to 30 wt% and a degree of vulcanization is 15 to 30 wt%; the alkaline solution contains at least one of sodium hydroxide, potassium hydroxide, sodium sulfite, sodium sulfide, sodium carbonate, sodium sulfate and sodium thiosulfate; more preferably, the alkaline solution comprises sodium hydroxide and at least one of sodium sulfite and sodium sulfide.
5. The production method according to any one of claims 1 to 4, wherein the solid-to-liquid ratio of the raw material to the alkaline solution is 1: 4-1: 20, preferably 1: 4-1: 10.
6. The method according to claim 3, wherein the amount of the enzyme bleaching enzyme is 0.2-2 wt% of the raw material, and the solid-to-liquid ratio is 1: 4-1: 10;
the enzyme used in the enzymatic bleaching process comprises one or more of xylanase, manganese peroxidase and laccase.
7. The method of claim 3, wherein in the oxidant solution, the oxidant is at least one of hydrogen peroxide, hypohalous acid or salt thereof, organic peroxyacids, sodium percarbonate, chlorine dioxide, oxygen, ozone, borohydride, and dithionite; preferably, the oxidant is any one of hydrogen peroxide, oxygen, ozone and chlorine dioxide; more preferably, in the oxidant solution, the mass content of the oxidant is 0.2-5 wt%, and the oxidant solution further contains 0.1-2.5 wt% of sodium hydroxide.
8. The method according to claim 1, wherein the delignified feedstock freezing temperature is-30 to 0 ℃ and the delignified feedstock thawing temperature is 20 to 100 ℃.
9. The method according to claim 1, wherein the wet bamboo chips are dried by any one of supercritical drying, freeze drying, vacuum oven drying and forced air drying; preferably freeze-dried.
10. The method of claim 9, wherein the freeze-drying further comprises a freezing medium, the freezing medium being water and/or t-butanol; tert-butanol is preferred.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110354860.5A CN114276975A (en) | 2021-03-30 | 2021-03-30 | Preparation method of hollow and multi-hollow hybrid cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110354860.5A CN114276975A (en) | 2021-03-30 | 2021-03-30 | Preparation method of hollow and multi-hollow hybrid cells |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114276975A true CN114276975A (en) | 2022-04-05 |
Family
ID=80868219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110354860.5A Pending CN114276975A (en) | 2021-03-30 | 2021-03-30 | Preparation method of hollow and multi-hollow hybrid cells |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114276975A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100662042B1 (en) * | 2006-04-25 | 2006-12-27 | 이권혁 | The production method and pulp maked bamboos |
| WO2008074220A1 (en) * | 2006-12-18 | 2008-06-26 | Hebei Jigao Chemical Fiber Co., Ltd. | A preparation method of a bamboo pulp |
| WO2009015556A1 (en) * | 2007-07-27 | 2009-02-05 | Shandong Tralin Paper Co., Ltd | Process for producing paper-making pulps from grasses and pulps obtained by the process |
| CN101864602A (en) * | 2009-08-06 | 2010-10-20 | 廖大中 | Method for preparing bamboo fibers by separating bamboo |
| CN106273203A (en) * | 2016-08-08 | 2017-01-04 | 雷春生 | A kind of preparation method of high toughness plastic ruler |
| CN109485737A (en) * | 2018-12-19 | 2019-03-19 | 国际竹藤中心 | A method of Cellulose nanocrystal is prepared using moso bamboo |
-
2021
- 2021-03-30 CN CN202110354860.5A patent/CN114276975A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100662042B1 (en) * | 2006-04-25 | 2006-12-27 | 이권혁 | The production method and pulp maked bamboos |
| WO2008074220A1 (en) * | 2006-12-18 | 2008-06-26 | Hebei Jigao Chemical Fiber Co., Ltd. | A preparation method of a bamboo pulp |
| WO2009015556A1 (en) * | 2007-07-27 | 2009-02-05 | Shandong Tralin Paper Co., Ltd | Process for producing paper-making pulps from grasses and pulps obtained by the process |
| CN101864602A (en) * | 2009-08-06 | 2010-10-20 | 廖大中 | Method for preparing bamboo fibers by separating bamboo |
| CN106273203A (en) * | 2016-08-08 | 2017-01-04 | 雷春生 | A kind of preparation method of high toughness plastic ruler |
| CN109485737A (en) * | 2018-12-19 | 2019-03-19 | 国际竹藤中心 | A method of Cellulose nanocrystal is prepared using moso bamboo |
Non-Patent Citations (3)
| Title |
|---|
| S. SUZUKI等: "Development of high strength bamboo paper using parenchyma cells", 《WIT TRANSACTIONS ON THE BUILT ENVIRONMENT》, vol. 97, pages 241 - 249 * |
| 叶利培: "竹材薄壁组织的物理分离及其用于制取低聚木糖的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 4, pages 024 - 455 * |
| 李卫林: "碱煮氧化工艺制备竹纤维及结构性能表征", 《林产工业》, vol. 58, no. 1, pages 6 - 10 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9121134B2 (en) | Process for production of oxidised cellulose pulp | |
| JP4586066B2 (en) | Pulp manufacturing method using bamboo and pulp manufactured using this method | |
| EP2576629B1 (en) | A novel method to produce microcellulose | |
| CN102947343B (en) | The manufacture of Microcrystalline Cellulose | |
| WO1998016682A2 (en) | Process for the co-production of dissolving-grade pulp and xylan | |
| CA2056605C (en) | Method of producing pulp | |
| WO2007102638A1 (en) | Method for producing xylose from bamboos | |
| CN104099794A (en) | Preparation method for nanocellulose | |
| CN108396591A (en) | A kind of preparation method of the high-strength nanometer film for having both ultraviolet shielding function | |
| CN114687234A (en) | Method for preparing fluff pulp by using bamboos and fluff pulp prepared by method | |
| CN109930416B (en) | Plant fiber environment-friendly material and preparation method thereof | |
| CN101934545B (en) | Method for manufacturing bamboo fibers | |
| CN109665511A (en) | A method of carbon nano-fiber aeroge is prepared by plant fiber | |
| CN114277598A (en) | Preparation method of hollow and porous hybrid cells and bamboo dissolving pulp | |
| CN115142263B (en) | Cationic bamboo cellulose nanofiber and preparation method thereof | |
| WO2012070072A2 (en) | A process for obtaining alpha-cellulose | |
| CN114276975A (en) | Preparation method of hollow and multi-hollow hybrid cells | |
| CN114277597A (en) | Method for separating bamboo fiber | |
| JP6444806B2 (en) | Dissolving pulp | |
| KR20010077423A (en) | Method of manufacturing a regenerated cellulose fiber from the rice straw | |
| KR20180083251A (en) | Cellulose production method | |
| JPS5898093A (en) | Pretreatment of cellulosic material for saccharification | |
| CN115260552B (en) | High-light-transmittance and high-haze holocellulose film material and preparation method thereof | |
| CN114645479B (en) | Preparation method of paper pulp | |
| CN115637601B (en) | Method for green extraction of high-purity cellulose nanofiber from shaddock ped |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |