CN101906214A - Method for preparing crosslinked spherical cellulose particles - Google Patents
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Abstract
The invention discloses a method for preparing crosslinked spherical cellulose particles, which comprises the following steps: (1) dissolving alpha-pulp or cotton serving as a raw material in aqueous solution of N-methyl morpholine oxide (NMMO) to prepare NMMO/cellulose/H2O solution; (2) adding a dispersant, an emulsifier and the NMMO/cellulose/H2O solution in a reaction kettle, heating the mixture with stirring to disperse the solution to form spherical beads, cooling, solidifying and obtaining spherical cellulose particles; (3) recovering the dispersant and NMMO; and (4) obtaining the crosslinked spherical cellulose particles. The method has the advantages that: the preparation process is simple and easy to industrialize; the raw materials are nontoxic, widely available, low in price and recyclable; and an environmentally-friendly production process is provided. The prepared crosslinked spherical cellulose particles are characterized in that: the shape is a spherical or ellipsoidal shape; the particle size ranges from 10 to 900mu m; the water content is 80 to 95 percent; the wet density is 1.02 to 1.1 g/ml; the pore size distribution of a macro porous structure ranges from 10nm to 1nm; the average pore size ranges from 100 to 500nm; and the bearable operation pressure ranges from 7 to 10bar.
Description
Technical field
This patent belongs to the functional polymer technical field, and particularly a kind of anti-phase suspension dispersion method of utilizing cleans the method for preparing crosslinked spherical cellulose particles.
Background technology
The development pole the earth of chemistry and material industry has promoted human civilization, but the reserves of oil, Sweet natural gas class resource are fewer and feweri, and the problems such as environmental pollution that industrialization brought are also constantly perplexing people.Simultaneously, the cellulose family natural macromolecular material is because of its reserves are huge, renewable, cheap, degradable, and advantage such as environmentally safe, causes people's attention day by day.The peculiar safety non-toxic of Mierocrystalline cellulose, wetting ability, biocompatibility, chirality and characteristics such as semi-rigid are very suitable for as chromosorb it.Mierocrystalline cellulose and derivative thereof have been widely used in a plurality of fields such as gel chromatography, ion-exchange chromatography, hydrophobic chromatography, affinity chromatography.The plain sorbent material of early stage commercial fibre is mainly based on the amorphous fine-particle shape, exist shortcomings such as back-pressure is big, pore structure is bad, hydraulic performance difference, and ball shaped cellulose pearl sorbent material has remedied these shortcomings just, become the main flow (Zhu Bairu that scholars study and use gradually, ball shaped cellulose preparation of adsorbent and applied research progress, fine chemistry industry [J] .1996, Vol.13, No.3,42～45).
The preparation of ball shaped cellulose generally is divided into following step: at first Mierocrystalline cellulose or its derivative are made solution (or molten state), more described cellulose solution are dispersed into drop, drop curing balling-up and cellulose regenerated.Mierocrystalline cellulose is by many β-1, and the straight-chain polysaccharide that the 4-glycosidic link is formed has very strong intramolecularly and intermolecular hydrogen bonding, and molecular chain is piled up closely, is difficult to melt-processed.Traditional viscose process is that Mierocrystalline cellulose is generated the cellulose sulfonate (viscose glue) of solubility after alkalization, aging and sulfonation, can produce a large amount of spent acid, salkali waste and toxic gas but prepare with viscose glue in the process of ball shaped cellulose.At present, the researchist has found some novel cellosolve systems again, as PF/DMSO, N
2O
4/ DMSO, LiCl/DMAc, NMMO/H
2O etc.Major part in these solvents does not still possess the condition of large-scale application, and NMMO/H
2O has advantages such as pollution-free, recyclable because of it, abroad large-scale application in the Lyocell fiber (Wu Cuiling etc., the research of novel organic cellulose solvent-NMMO. the journal .2005 of Lanzhou University of Science ﹠ Technology, 31 (2): 73-76; Gu Guangxin etc., the sign of Mierocrystalline cellulose/NMMO solution dissolving method and solution thereof. Donghua University's journal (natural science edition) [J] .2001,16 (5): 127-131).But the report that is applied to the preparation of ball shaped cellulose sorbent material is less, and exists problems such as prepared pearl body particle diameter is bigger.The formation of drop has two kinds of methods substantially: a kind of gunite that is called needs special equipment; Another kind is similar to suspension polymerization, and the solution of Mierocrystalline cellulose and derivative thereof is dispersed in immiscible medium, forms in " oil-in-water " or " water-in-oil " system.Difference has acid precipitation method, salt precipitation method, crosslinking, heating method, method of cooling, dilution method etc. according to the forming process of different initiator, different solvents system and different drops in the curing of drop.Renovation process is also different according to the difference of initiator, and acid reclaiming process, saponification method of reproduction, thermal regeneration method etc. should be arranged mutually.Among these preparation methods, with the cellulose sulfonate viscose as raw material, advantage with low price, convenient sources, therefore by external institute of company industrialization, but produce a large amount of spent acid alkali lye, waste gas and waste material etc. in the preparation process, cause very big pollution to environment, therefore restricted the development of cellulose grain industry.
Summary of the invention
The objective of the invention is: overcome the shortcoming of prior art, a kind of method for preparing crosslinked spherical cellulose particles that the convenient sources of supplying raw materials, low price and preparation technology are simple, environment friendly and pollution-free.
For achieving the above object, the technical scheme of taking is: with pulp or cotton is raw material, is raw material with the aqueous solution of N-methylmorpholine-N-oxide compound (NMMO), dissolving preparation NMMO/ Mierocrystalline cellulose/H
2O solution adopts the anti-phase suspension dispersion method to prepare spherical cellulose grain, with described NMMO/ Mierocrystalline cellulose/H
2O solution joins in the emulsion that is formed by liquid dispersant and emulsifying agent, and elevated temperature makes it be dispersed into spherical beaded, and cooling curing again, crosslinking reaction make crosslinked spherical cellulose particles and reclaim starting material.
Clean the preparation crosslinked spherical cellulose particles with the anti-phase suspension dispersion method, specifically comprise four steps:
(1) NMMO/ Mierocrystalline cellulose/H
2The preparation of O solution:
In mass, take by weighing 1 part of cellulose materials such as pulp or cotton, add NMMO aqueous solution 7-60 part, antioxidant 0.001-0.05 part under 80-110 ℃ of condition, vacuumizes while stirring, become the filemot solution of transparent and homogeneous until system, obtain the NMMO/ Mierocrystalline cellulose/H of different content of cellulose
2O solution.
Antioxidant is one or more a mixture in pyrogallol, Tenox PG, butylated hydroxy anisole, butylated hydroxytoluene, tertiarybutylhydroquinone, saccharosonic acid, the oxalic acid, when two or more mixing, can be arbitrary proportion.
(2) anti-phase suspension disperses the legal system ball:
In mass, in reactor, add dispersion agent 3-7 part, emulsifying agent 0.02-0.25 part, NMMO/ Mierocrystalline cellulose/H
21 part of O solution, warming while stirring are incubated and are cooled to 25 ℃ after 2 hours to 100-110 ℃, add the dilution of 1 part of low boiling point solvent then, filter, with cellulose grain with about 20 times of washed with de-ionized water, clean to till the water surface non-foam clarification of water, obtain spherical cellulose grain.
Dispersion agent is two or more a mixture in the polypropylene glycol (PPG) of different molecular weight, described different molecular weight polypropylene glycol is meant PPG600, PPG800, PPG1000, PPG1500, PPG2000, PPG3000, PPG4000, PPG6000, PPG8000, PPG10000, and the polypropylene glycol of optimal effectiveness is meant PPG1500, PPG2000, PPG3000, PPG4000, PPG6000, PPG8000.
Emulsifying agent is a kind of in nonionogenic tenside, the aniorfic surfactant, perhaps their mixture.Described nonionogenic tenside is a kind of among Tween20, Tween40, Tween60, Tween80, Tween85, Span20, Span40, Span60, the Span80.Anion surfactant is a kind of in sodium oleate, the potassium oleate.
Low boiling point solvent is meant a kind of in ethanol, propyl alcohol, the acetone.
(3) recovery of dispersion agent and NMMO:
Low boiling point solvent is removed and reclaimed in above-mentioned filtrate distillation, leave standstill phase-splitting, the upper strata is a dispersion agent, and lower floor is the NMMO aqueous solution.After removing residual moisture, the dispersion agent distillation can utilize again.The NMMO of the lower floor solution of cellulose grain scavenging solution and recovery is merged, adds the flocculation agent flocculation, remove by filter precipitation, then filtrate is crossed zwitterion post removal of impurities decolouring after, can utilize again.
Flocculation agent is meant a kind of in aluminum chloride, poly-sial, sodium polyacrylate, the polyacrylamide.
(4) crosslinked
Get 1 part of cellulose grain through above-mentioned processing, with the activation of 2-5 part 7% aqueous sodium hydroxide solution, 0.1-5 part epoxy chloropropane is as linking agent, and 60 ℃ of reaction 3h add the acid neutralization, and suction filtration is cleaned with acetone and deionized water, obtains crosslinked spherical cellulose particles.
The invention has the beneficial effects as follows: clean the preparation crosslinked spherical cellulose particles with the anti-phase suspension dispersion method, described spherical cellulose grain is a regenerated cellulose, outward appearance is sphere or elliposoidal, and particle size distribution range is 10-40 μ m, 40-150 μ m, 150-300 μ m, 300-600 μ m, 600-900 μ m; Water ratio 80%-95%, wet true density 1.02-1.1g/ml has macroporous structure, and pore size distribution is 10nm-1 μ m, and mean pore size is 100-500nm, can the working pressure of anti-7-10bar.Preparation technology of the present invention is simple and easy to industrialization, and advantages of nontoxic raw materials wide material sources price is low and can recycle, is a kind of production technique of environmental protection.
Description of drawings
Fig. 1: preparation spherical cellulose grain process flow sheet;
Fig. 2: the microphotograph of spherical cellulose grain;
Fig. 3: the graph of pore diameter distribution of spherical cellulose grain.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.Step of preparation process of the present invention is shown in Fig. 1, and the outward appearance of spherical cellulose grain and pore size distribution are illustrated in Fig. 2 and Fig. 3.
The non-special declaration of material is mass percent among the embodiment.
(1) NMMO/ Mierocrystalline cellulose/H
2The preparation of O solution:
Get purified cotton 100 gram, add the 60%NMMO aqueous solution 3468 grams, Tenox PG 2g under 80-110 ℃ of condition, vacuumizes while stirring, becomes the filemot solution of transparent and homogeneous until system, promptly gets content of cellulose and be NMMO/ Mierocrystalline cellulose/H of 4%
2O solution.
(2) anti-phase suspension disperses the legal system ball:
In reactor, add 2kg PPG6000 and the mixture (mass ratio 1: 1) of PPG800, the NMMO/ Mierocrystalline cellulose/H of 450g 4% content of cellulose
2O solution and 50g Tween40, warming while stirring is incubated and is cooled to 25 ℃ after 2 hours to 100-110 ℃, adds the 500ml alcohol dilution, filters.With a large amount of (the about 20 times) washed with de-ionized water of the cellulose grain that leaches, till water surface non-foam clarification of water, obtain spherical cellulose grain.
(3) recovery of NMMO and PPG:
Ethanol is removed and reclaimed in above-mentioned filtrate distillation, leave standstill phase-splitting, the upper strata is PPG, and lower floor is the NMMO aqueous solution.After removing residuary water, the PPG distillation can utilize again.The NMMO of the lower floor solution of cellulose grain scavenging solution and recovery is merged, and press the 7ppm amount and add the polyacrylamide flocculation, remove by filter precipitation, then filtrate is crossed respectively after the removal of impurities of zwitterion post decolours, can utilize again.
(4) crosslinked:
Take by weighing the spherical cellulose grain of preparation in the 200g above-mentioned steps (2), add 7% sodium hydroxide solution 1000ml, mixed 20 minutes, under 60 ℃, add the 100g epoxy chloropropane, react that adding 2.5N concentrated hydrochloric acid is neutralized to neutrality after 3 hours.Acetone and 20 times of (cellulose grain weight) washed with de-ionized water with 5 times (cellulose grain weight) are clean, obtain crosslinked spherical cellulose particles.
After measured, it is sphere or elliposoidal that this method obtains the external sight of crosslinked spherical cellulose particles pearl, particle size distribution range 10-40 μ m (massfraction 16%), 40-150 μ m (54%), 150-600 μ m (18%), 600-900 μ m (12%); Water ratio 91%, wet true density 1.02g/ml has macroporous structure, and pore size distribution is 10nm-1 μ m, and mean pore size is 440nm, can the working pressure of anti-7.2bar.
(1) NMMO/ Mierocrystalline cellulose/H
2The preparation of O solution:
Get purified cotton 100 gram, add the 60%NMMO aqueous solution 3468 grams, pyrogallol 2g under 80-110 ℃ of condition, vacuumizes while stirring, becomes the filemot solution of transparent and homogeneous until system, content of cellulose is NMMO/ Mierocrystalline cellulose/H of 4%
2O solution.
(2) anti-phase suspension disperses the legal system ball:
In reactor, add 2kg PPG3000 and the mixture (mass ratio 1: 1) of PPG1000, the NMMO/ Mierocrystalline cellulose/H of 330g 6% content of cellulose
2The mixed surfactant of O solution and 50g Tween80 and Span80 (mass ratio 1: 1), warming while stirring is to 100-110 ℃, be incubated and be cooled to 25 ℃ after 2 hours, add the dilution of 350mL propyl alcohol, filter, the cellulose grain that leaches with a large amount of washed with de-ionized water, is obtained spherical cellulose grain.
(3) recovery of NMMO and PPG:
Press and embodiment 1 step (3) same operation method reclaimer operation.
(4) crosslinked:
Take by weighing the spherical cellulose grain of preparation in the 200g above-mentioned steps (2), add 7% sodium hydroxide solution 1000ml, mixed 20 minutes, under 60 ℃, add the 200g epoxy chloropropane, react that adding 2.5N concentrated hydrochloric acid is neutralized to neutrality after 3 hours.Clean with acetone and a large amount of washed with de-ionized water, obtain crosslinked spherical cellulose particles.
After measured, it is sphere or elliposoidal that this method obtains the crosslinked spherical cellulose particles outward appearance, particle size distribution range 10-40 μ m (massfraction 5.5%), 40-150 μ m (50%), 150-600 μ m (30.5%), 600-900 μ m (14%); Water ratio 88.6%, wet true density 1.02g/ml has macroporous structure, pore size distribution 10nm-1 μ m, mean pore size is 360nm, can the working pressure of anti-8.1bar.
Embodiment 3
(1) NMMO/ Mierocrystalline cellulose/H
2The preparation of O solution:
Get cotton pulp dregs of rice 120g, add 60%NMMO aqueous solution 2717g, saccharosonic acid 3.6g under 90-110 ℃ of condition, vacuumizes while stirring, becomes the filemot solution of transparent and homogeneous until system, promptly gets content of cellulose and be NMMO/ Mierocrystalline cellulose/H of 6%
2O solution.
(2) anti-phase suspension disperses the legal system ball:
In reactor, add 2kg PPG1500 and the mixture (mass ratio 1: 1) of PPG2000, the NMMO/ Mierocrystalline cellulose/H of 400g 6% content of cellulose
2The mixed surfactant of O solution and 50g Tween80 and sodium oleate (mass ratio 1: 1), warming while stirring are incubated 2 hours to 100-110 ℃, are cooled to 25 ℃, add the 450mL acetone diluted then, filter.The cellulose grain that leaches with a large amount of washed with de-ionized water, is obtained spherical cellulose grain.
(3) recovery of NMMO and PPG:
Press and embodiment 1 step (3) same procedure reclaimer operation.
(4) crosslinked:
Take by weighing the spherical cellulose grain of preparation in the 200g above-mentioned steps (2), add 7% sodium hydroxide solution 1000ml, mixed 20 minutes, under 60 ℃, add the 300g epoxy chloropropane, react that adding 2.5N concentrated hydrochloric acid is neutralized to neutrality after 3 hours.Clean with acetone and a large amount of washed with de-ionized water, obtain crosslinked spherical cellulose particles.
After measured, it is sphere or elliposoidal that this method obtains the crosslinked spherical cellulose particles outward appearance, particle size distribution range 40-150 μ m (15%), 150-300 μ m (37%), 300-600 μ m (25%), 600-900 μ m (23%); Water ratio 85%, wet true density 1.04g/ml has macroporous structure, and pore size distribution is 10nm-1 μ m, and mean pore size 260nm can withstand voltage 9.2bar.
Embodiment 4
(1) NMMO/ Mierocrystalline cellulose/H
2The preparation of O solution:
Get the cotton pulp dregs of rice 120 gram, add the 60%NMMO aqueous solution 2717 grams, butylated hydroxy anisole 4g under 80-110 ℃ of condition, vacuumizes while stirring, becomes the filemot solution of transparent and homogeneous until system, content of cellulose is NMMO/ Mierocrystalline cellulose/H of 6%
2O solution.
(2) anti-phase suspension disperses the legal system ball:
In reactor, add 2kg PPG1500 and the mixture (mass ratio 1: 1) of PPG8000, the NMMO/ Mierocrystalline cellulose/H of 450g 6% content of cellulose
2The mixed surfactant of O solution and 40g Tween80 and Span80 (mass ratio 1: 1), warming while stirring to 100 are incubated 2 hours to 110 ℃.Be cooled to 25 ℃, add the 500ml alcohol dilution, filter.The cellulose grain that leaches with a large amount of washed with de-ionized water, is obtained spherical cellulose grain.
(3) recovery of NMMO and PPG:
Remove flocculation agent and consumption thereof by adding the 7ppm weight polyacrylamide, change into and adding outside the poly-sial of 20ppm amount, all the other all by with embodiment 1 step (3) same procedure reclaimer operation.
(4) crosslinked:
Take by weighing the spherical cellulose grain of preparation in the 200g above-mentioned steps (2), add 7% sodium hydroxide solution 1000ml, mixed 20 minutes, under 60 ℃, add the 100g epoxy chloropropane, react that adding 2.5N concentrated hydrochloric acid is neutralized to neutrality after 3 hours.Clean with acetone and a large amount of washed with de-ionized water, obtain crosslinked spherical cellulose particles.
After measured, it is sphere or elliposoidal that this method obtains the crosslinked spherical cellulose particles outward appearance, particle size distribution range 10-40 μ m (18.6%), 40-150 μ m (35%), 150-300 μ m (26.1%), 300-600 μ m (15%), 600-900 μ m (5.3%); Water ratio 89%, wet true density 1.04g/ml has macroporous structure, and pore size distribution is 10nm-1 μ m, and mean pore size 300nm can withstand voltage 8.7bar.
(1) NMMO/ Mierocrystalline cellulose/H
2The preparation of O solution:
Get the cotton pulp dregs of rice 120 grams, add the 60%NMMO aqueous solution 1994 grams, butylated hydroxytoluene 2g, oxalic acid 2g under 80-110 ℃ of condition, vacuumizes while stirring, become the filemot solution of transparent and homogeneous until system, content of cellulose is NMMO/ Mierocrystalline cellulose/H of 8%
2O solution.
(2) anti-phase suspension disperses the legal system ball:
In reactor, add 2kg PPG2000 and the mixture (mass ratio 1: 1) of PPG4000, the NMMO/ Mierocrystalline cellulose/H of 450g 4% content of cellulose
2O solution and 50g Tween40, warming while stirring to 100 is incubated 2 hours to 110 ℃.Be cooled to 25 ℃, add the 500ml alcohol dilution, filter.The cellulose grain that leaches with a large amount of washed with de-ionized water, is obtained spherical cellulose grain.
(3) recovery of NMMO and PPG:
Remove flocculation agent and consumption thereof by adding the 7ppm weight polyacrylamide, change into and adding outside the poly-sial of 20ppm amount aluminum chloride, all the other all by with embodiment 1 step (3) same procedure reclaimer operation.
(4) crosslinked:
Take by weighing the spherical cellulose grain of preparation in the 200g above-mentioned steps (2), add 7% sodium hydroxide solution 1000ml, mixed 20 minutes, under 60 ℃, add the 100g epoxy chloropropane, react that adding 2.5N concentrated hydrochloric acid is neutralized to neutrality after 3 hours.Clean with acetone and a large amount of washed with de-ionized water, obtain crosslinked spherical cellulose particles.
After measured, it is sphere or elliposoidal that this method obtains the crosslinked spherical cellulose particles outward appearance, particle size distribution range 40-150 μ m (48%), 150-600 μ m (34%), 600-900 μ m (18%); Water ratio 92%, wet true density 1.06g/ml has macroporous structure, and pore size distribution is 10nm-1 μ m, and mean pore size 210nm can withstand voltage 9.3bar.
Embodiment 6
(1) NMMO/ Mierocrystalline cellulose/H
2The preparation of O solution:
Get the cotton pulp dregs of rice 120 gram, add the 60%NMMO aqueous solution 1994 grams, tertiarybutylhydroquinone 2g under 80-110 ℃ of condition, vacuumizes while stirring, becomes the filemot solution of transparent and homogeneous until system, content of cellulose is NMMO/ Mierocrystalline cellulose/H of 8%
2O solution.
(2) anti-phase suspension disperses the legal system ball:
In reactor, add 2kg PPG2000, the mixture (mass ratio 1: 1: 1) of PPG3000, PPG4000, the NMMO/ Mierocrystalline cellulose/H of 450g 8% content of cellulose
2O solution and 50g Tween40, warming while stirring to 100 is incubated 2 hours to 110 ℃.Be cooled to 25 ℃, add the 500ml alcohol dilution, filter.The cellulose grain that leaches with a large amount of washed with de-ionized water, is obtained spherical cellulose grain.
(3) recovery of NMMO and PPG:
Except that flocculation agent and add-on thereof change into: press the 10ppm amount and add the sodium polyacrylate flocculation, all the other and embodiment 1 step (3) same procedure reclaimer operation.
(4) crosslinked:
Take by weighing the spherical cellulose grain of preparation in the 200g above-mentioned steps (2), add 7% sodium hydroxide solution 1000ml, mixed 20 minutes, under 60 ℃, add the 300g epoxy chloropropane, react that adding 2.5N concentrated hydrochloric acid is neutralized to neutrality after 3 hours.Clean with acetone and a large amount of washed with de-ionized water, obtain crosslinked spherical cellulose particles.
After measured, it is sphere or elliposoidal that this method obtains the crosslinked spherical cellulose particles outward appearance, particle size distribution range 40-50 μ m (44%), 150-600 μ m (37%), 600-900 μ m (19%); Water ratio 82.5%, wet true density 1.07g/ml has macroporous structure, and pore size distribution is 10nm-1 μ m, and mean pore size 130nm can withstand voltage 9.8bar.
Claims (8)
1. method for preparing crosslinked spherical cellulose particles, it is characterized in that: step is:
(1) NMMO/ Mierocrystalline cellulose/H
2The preparation of O solution:
In mass, take by weighing 1 part of cellulose materials such as pulp or cotton, add NMMO aqueous solution 7-60 part, antioxidant 0.001-0.05 part under 80-110 ℃ of condition, vacuumizes while stirring, becomes the filemot solution of transparent and homogeneous until system;
(2) the anti-phase suspension dispersion method prepares spherical cellulose grain:
In mass, in reactor, add dispersion agent 3-7 part, emulsifying agent 0.02-0.25 part, NMMO/ Mierocrystalline cellulose/H
21 part of O solution, warming while stirring are incubated and are cooled to 25 ℃ after 2 hours to 100-110 ℃, add 1 part of low boiling point solvent dilution then, use a large amount of washed with de-ionized water, till water surface non-foam clarification of water;
(3) recovery of dispersion agent and NMMO:
Low boiling point solvent is removed and is reclaimed in the distillation of described step (2) filtrate, leave standstill phase-splitting, the upper strata is a dispersion agent, lower floor is the NMMO aqueous solution, and dispersion agent can utilize again after residual moisture was removed in distillation, with the NMMO of the lower floor solution merging of cellulose grain scavenging solution and recovery, add the flocculation agent flocculation, remove by filter precipitation, filtrate is utilized after crossing zwitterion post removal of impurities decolouring again;
(4) crosslinked:
Get 1 part of cellulose grain of handling through described step (2), with the activation of 2-5 part 7% aqueous sodium hydroxide solution, 0.1-5 part epoxy chloropropane is as linking agent, 60 ℃ of reaction 3h add the acid neutralization, suction filtration, clean with acetone and deionized water, obtain crosslinked spherical cellulose particles.
2. according to the described a kind of method for preparing crosslinked spherical cellulose particles of claim 1, it is characterized in that: the described antioxidant of step (1) is one or more a mixture in pyrogallol, Tenox PG, butylated hydroxy anisole, butylated hydroxytoluene, tertiarybutylhydroquinone, saccharosonic acid, the oxalic acid, when two or more mixing, can be arbitrary proportion.
3. according to the described a kind of method for preparing crosslinked spherical cellulose particles of claim 1, it is characterized in that: the described dispersion agent of step (2) is two or more a mixture in the polypropylene glycol (PPG) of different molecular weight.
4. according to the described a kind of method for preparing crosslinked spherical cellulose particles of claim 3, it is characterized in that: described different molecular weight polypropylene glycol is meant PPG600, PPG800, PPG1000, PPG1500, PPG2000, PPG3000, PPG4000, PPG6000, PPG8000 or PPG10000, and the polypropylene glycol of optimal effectiveness is meant PPG1500, PPG2000, PPG3000, PPG4000, PPG6000, PPG8000.
5. according to the described a kind of method for preparing crosslinked spherical cellulose particles of claim 1, it is characterized in that: the described emulsifying agent of step (2) is a kind of in nonionogenic tenside, the aniorfic surfactant, perhaps their mixture.
6. according to the described a kind of method for preparing crosslinked spherical cellulose particles of claim 5, it is characterized in that: described nonionogenic tenside is meant a kind of among Tween20, Tween40, Tween60, Tween80, Tween85, Span20, Span40, Span60, the Span80: described aniorfic surfactant is meant a kind of in sodium oleate, the potassium oleate.
7. according to the described a kind of method for preparing crosslinked spherical cellulose particles of claim 1, it is characterized in that: the described low boiling point solvent of step (2) is meant a kind of in ethanol, propyl alcohol, the acetone.
8. according to the described a kind of method for preparing crosslinked spherical cellulose particles of claim 1, it is characterized in that: the described flocculation agent of step (3) is meant a kind of in aluminum chloride, poly-sial, sodium polyacrylate, the polyacrylamide.
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| CN106116846A (en) * | 2016-06-24 | 2016-11-16 | 苏州市泰盛农业科技有限公司 | A kind of Cuiguan pear plantation fertilizer improving soil property |
| CN107326022A (en) * | 2017-03-29 | 2017-11-07 | 东北林业大学 | A kind of method of silanization magnetic cellulose microsphere fixed fat enzyme |
| CN108745219A (en) * | 2018-06-20 | 2018-11-06 | 四川大学 | A kind of cellulose microsphere preparation method of novel high intensity and even intensity |
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| 林春香等: ""一种新型球形纤维素吸附剂对水中Ni2+的吸附行为"", 《纤维素科学与技术》 * |
| 黄建辉等: ""NMMO法球形纤维素珠体的制备及粒径分布的研究"", 《纤维素科学与技术》 * |
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| CN105829351A (en) * | 2013-10-15 | 2016-08-03 | 连津格股份公司 | Three-dimensional cellulose moulded body, method for the production thereof and use of the same |
| CN105829351B (en) * | 2013-10-15 | 2019-05-10 | 连津格股份公司 | Three-dimensional fiber element formed body, Its Preparation Method And Use |
| CN106116846A (en) * | 2016-06-24 | 2016-11-16 | 苏州市泰盛农业科技有限公司 | A kind of Cuiguan pear plantation fertilizer improving soil property |
| CN107326022A (en) * | 2017-03-29 | 2017-11-07 | 东北林业大学 | A kind of method of silanization magnetic cellulose microsphere fixed fat enzyme |
| CN108745219A (en) * | 2018-06-20 | 2018-11-06 | 四川大学 | A kind of cellulose microsphere preparation method of novel high intensity and even intensity |
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