CN1233716C - Crosslinked spheric regenerated cellulose beads and clean preparation thereof by program cooling counterphase suspension - Google Patents
Crosslinked spheric regenerated cellulose beads and clean preparation thereof by program cooling counterphase suspension Download PDFInfo
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- CN1233716C CN1233716C CN 03118969 CN03118969A CN1233716C CN 1233716 C CN1233716 C CN 1233716C CN 03118969 CN03118969 CN 03118969 CN 03118969 A CN03118969 A CN 03118969A CN 1233716 C CN1233716 C CN 1233716C
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Abstract
The present invention discloses crosslinked spherical regenerated cellulose bead bodies and a clean preparation method thereof by a programmed temperature drop reversed-phase suspension technology. The method comprises the following steps: paper pulp or cotton is dissolved in a water solution of N-methylmorpholine-N-oxide at a suitable temperature to form a cellulose-NMMO-water solution with suitable mass fraction; the cellulose-NMMO-water solution is dispersed in a medium prepared from 1.0% to 50% of NMMO water solution, a surface active agent, etc. which are unmixable with each other, the cellulose-NMMO-water solution is solidified through an external force and programmed temperature drop at suitable pressure to prepare the crosslinked spherical regenerated cellulose bead bodies with the average pore diameter of 5 to 30 nm, the specific surface area of 120 to 650 m<2>/g, the water ratio of 50% to 75%, the skeletal density of 0.91 to 1.30 g/ml, the apparent density of 0.45 to 0.81 g/ml, the pore volume of 0.15 to 1.12 ml/g and the porosity of 80% to 96%, and the particle diameters of the crosslinked spherical regenerated cellulose bead bodies are different. The present invention has the advantages of simple manufacturing technology and nontoxicity. The product has the advantages of good swelling resisting performance, and good chemical degradation and biological degradation resisting capability.
Description
Technical field:
The invention belongs to functional high polymer material field, specially refer to the programmed cooling reversed phase suspension technique and prepare crosslinked spherical regenerated cellulose pearl body and clean technology.
Background technology:
The world today, the deposit of oil, natural gas source is limited, and their research, development and utilization is on the rise to the influence that ball ecological environment brings, and this has impelled is that the macromolecular material of raw material is greatly developed with natural resource.Mierocrystalline cellulose is natural resource the abundantest on the earth, that can recover, have inexpensive, degradable and environment do not produced characteristics such as pollution, so countries in the world is all attached great importance to cellulosic research and development.
Mierocrystalline cellulose is by many β-1, and the straight-chain polysaccharide that the 4-glycosidic link is formed can pass through a series of chemical modification, produces the functional high molecule material of different purposes.The development and the application of cellulose adsorbent and ion-exchanger start from the beginning of the fifties, have the Mierocrystalline cellulose commodity selling of multiple brand and series at present both at home and abroad, because the limitation of preparation means, plain sorbent material of commercial fibre and ion-exchanger mostly are powdery or microgranular greatly, and pore structure is not so good, this just restricts its use range greatly, and the ball shaped cellulose sorbent material has just in time remedied the shortcoming of existing goods, can control cell size, granularity, it is big to have specific surface area, advantages such as transparent performance and hydraulic performance are good, be easy to operate on processing and the suitable post, and can be used to analyzing blood, remove the antigen in the blood plasma, the absorption serum protein, the separation and purification bacterial, preparation and separating chiral compound, the purifying chloroplast DNA, adsorbing metal ions, separate transition metal ion, reclaim noble metal etc., the interest that therefore relevant preparation and applied research cause the lot of domestic and international researcher.
Ball shaped cellulose preparation of adsorbent method generally can be divided into following step: cellulosic dissolving; The preparation of cellulose bead body is comprising the regeneration of curing that cellulose solution is dispersed into spherical drop, drop and cellulose bead body; Spherical regenerated cellulose functionalized.The solvent that is used for dissolving cellulos at present is mainly by cuprammonium complexing solvent, cadmium ethylenediamine complexing solvent and PF/DMSO, N
2O
4/ DMSO, LNH
3/ NH
4SCN, LiCl/DMAc equal solvent, because the solvent that has is still at the experimental stage, although existing manufacturing feasibility and the prospect of realizing that has, but can't be as the stock liquid of preparation cellulose bead body, therefore the lot of domestic and international researcher has been selected inexpensively, and raw material sources viscose easily prepare the cellulose bead body
[1-6]But viscose prepares a large amount of waste liquid, waste gas and the waste materials of generation in the cellulose bead body process, causes serious pollution to environment, and has restricted the development of ball shaped cellulose sorbent material to a certain extent.
Reference:
1.Minghua Liu，Xinshen Zhang，Yun Deng and Huaiyu Zhan.Removal and recovery of chromium(III)fromaqueous solutious by a spheroidal cellulose adsorbent.Water Environment Research，2001，73(3)：322-328
2.Minghua Liu，YunDeng，Huaiyu Zhan，Xinshen Zhang.Adsorption and desorption of copper(II)fromsolutions on a new spherical cellulose adsorbent J.Appl.Polym.Sci.，2002，84：478-485
3.Minghua Liu，Xinshen Zhang.Automatic on-line determination of trace chromium(VI)ion inchromium(III)-bearing samples by reverse adsorption process.JSLTC，2002，86：1-5
4.Passate R，Schwalbe H，Krieg M，et al.Preparation of spherical cellulosemoldings[P].Ger.(East)DD291,329，1991
5.Fujita M，Watanabe N，Satota N.Cellulose-based porous and spherical particles[P].Jpn.Kokai Jokkyo Koho Jp 03,170,501，1991
6.Laszleiewicz B，Struszczyk H，Skorecka-Kubicka H，et al.manufacture of microcrystalline cellulose[P].Pol.PL 139,735，1987
Summary of the invention:
The objective of the invention is to overcome the deficiencies in the prior art, the crosslinked spherical regenerated cellulose pearl body and the method for production thereof of a series of different-grain diameters are provided, promptly utilize N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide, abbreviation NMMO) the aqueous solution is that the direct dissolving cellulos of solvent is made cellulose solution, adopt the programmed cooling reversed phase suspension technique to prepare crosslinked spherical regenerated cellulose pearl body then and reclaim solvent, the whole process of preparation of cellulose bead body is a process of dissolving and solidifying, manufacturing process is simple, produce not have and poison, solvent is nontoxic, can reclaim, and non-environmental-pollution, be one and clean, environmentally friendly technology.
A series of different-grain diameters provided by the present invention crosslinked spherical regenerated cellulose pearl body, adopt direct dissolving cellulos to make cellulose solution, directly prepare crosslinked spherical regenerated cellulose pearl body with the programmed cooling reversed phase suspension technique then, the particle size distribution range that it is characterized in that described crosslinked spherical regenerated cellulose pearl body is respectively 1～10 μ m, 10～40 μ m, 40～80 μ m, 80～120 μ m, 120～200 μ m, mean pore size is 5～30nm, and specific surface area is 120～650m
2/ g, water ratio 50%～75%, skeletal density 0.91～1.30g/ml; Apparent density 0.45～0.81g/ml, pore volume 0.15～1.12ml/g, cell size 80%～96%.And have mechanical property, thermostability and swell-resistant energy, resistance of oxidation, antibiont degradation capability and an antiacid alkaline degradation ability preferably.
The preparation technology of above-mentioned crosslinked spherical cellulose pearl body comprises three steps: the recovery of cellulosic dissolving, programmed cooling anti-phase suspension and solvent, and concrete technology is as follows:
(1) cellulosic dissolving
Raw material and prescription (massfraction):
Paper pulp or cotton: 0.1～8%
NMMO·H
2O：87～99％
Stablizer: 0.1～5%
Cellulose dissolution processing step and processing parameter: paper pulp or cotton are put into Sheng N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 80～100 ℃, solubilizing reaction 30～120min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 0.1%～8.0%, add an amount of stablizer.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
Raw material and prescription (massfraction):
Above-mentioned cellulose solution: 1.0～32%
The 1.0%-50%NMMO aqueous solution: 1.0～30%
Tensio-active agent: 0.1～5.0%
Dispersion agent: 0.1%～1.5%
Low boiling point solvent: 30～75%
Activator: 0.1～5.0%
Linking agent: 0.1～5.0%
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish in the reactor of automatic feeding device of constant temperature system and add 1.0%～50%NMMO aqueous solution respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent etc., after stirring, slowly the dropping massfraction is Mierocrystalline cellulose-NMMO-aqueous solution of 0.1%～8.0%, in 30～60min, dropwise, and rotating speed is controlled at 20～400r/min, temperature of reaction in the reinforced process is 55～95 ℃, after adding material temperature is controlled at 45～85 ℃, behind reaction 45～75min, continue to be cooled to 35～65 ℃, behind reaction 30～60min, cooling again, reduce to normal temperature, total is crosslinked always, be 120～360min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step can carry out under 1 to 10 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 25～45 ℃, vacuum degree control is at 0.05～0.1mPa, reclaim low boiling point solvent, the rate of recovery can reach 80%-91%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 55～75 ℃, vacuum degree control is at 0.05～0.1mPa, remove portion water, after further filtration, ultrafiltration or the ion-exchange, promptly get N-methylmorpholine-N-oxide compound, its rate of recovery can reach 87%～95%.This processing step can carry out under normal pressure.
In this technology, cellulosic material is paper pulp or cotton, wherein paper pulp comprises with materials such as bagasse, Pinus massoniana Lamb, bamboo, rice straw, reeds being that raw material is made by sulphate process, sulphite process or alkaline process and through the paper pulp behind chemistry or the bio-bleaching, deinked waste paper paper pulp and disassociation old paper stock etc., cotton is mainly common cotton, comprising linters and absorbent cotton etc.; Solvent is N-methylmorpholine-N-oxide compound, and water ratio is 4～50%; Stablizer is Propylgallate, oxalic acid, sodium oxalate, potassium oxalate, saccharosonic acid, diethylamide, methylethyl ketoxime and composition thereof etc., can select wherein one or more mixtures as required, when selecting two or more mixtures to mix, but its blending ratio arbitrary proportion, add-on are 0.1～5%; Employed solvent is the N-methylmorpholine-N-oxide water solution of different concns and the mixture of other low boiling point solvent in the dispersion medium, the concentration of N-methylmorpholine-N-oxide water solution is 1.0%～50%, and low boiling point solvent is hexanaphthene, isohexane, hexane, 97
#Gasoline, 200
#Gasoline, kerosene etc. can be selected wherein one or more mixtures as required, when selecting two or more mixtures to mix, but its blending ratio arbitrary proportion; Tensio-active agent is oleic acid, Arlacelc, Arlace160, Span20, Span40, Span60, Span80, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, Tween20, Tween 40, Tween 60, Tween 80, sulfonated castor oil etc., can select wherein one or more mixtures as required, when selecting two or more mixtures to mix, but its blending ratio arbitrary proportion, add-on are 0.1～5.0%; Dispersion agent is Jian formula Tan Suan Magnesium, calcium phosphate powder, gelatin, polyvinyl alcohol, acid polyethylene, polyvinylpyrrolidone, phenolic aldehyde and urea aldehyde polycondensate and cellulose ethers etc., can select wherein one or more mixtures as required, when selecting two or more mixtures to mix, but its blending ratio arbitrary proportion, add-on are 0.1%～1.5%; Activator is alkaline matters such as sodium hydroxide, potassium hydroxide, and add-on is 0.1～5.0%; Linking agent is formaldehyde and derivative (comprising propenal, succinic aldehyde, melamine formaldehyde (MF) etc.) thereof, epoxy chloropropane, 1,3-two chloro-2-propyl alcohol, three isonitrile acid etc., can select wherein one or more mixtures as required, when selecting two or more mixtures to mix, but its blending ratio arbitrary proportion, add-on are 0.1～5.0%.
The present invention has the following advantages and positively effect:
1. utilize clean, environmentally friendly technology replaces traditional adhering process to prepare spherical cellulose bead, and in the preparation process of pearl body, can reclaim NMMO and low boiling point solvent, reduce the production cost of cellulose bead body greatly, make the cellulose bead physical efficiency of developing realize industrialization, move towards market from the laboratory.
2. the high added value environmentfriendly products of developing-crosslinked spherical regenerated cellulose pearl body, not only eliminated insoluble in the traditional technology " three wastes " pollution problem, and widened the development approach of functional high molecule material and environmentfriendly products, promote the development of functional high molecule material and environmental protection industry.
3. develop the crosslinked spherical regenerated cellulose pearl body of different-grain diameter, make it to be suitable for different purposes, as the removal and the hemanalysis of undesirable components in the blood, the separation and purification of various enzymes, the separation and purification of medicine, biochemical engineering material and usual protein etc.In addition, also can be used as stationary phase and the solid phase synthesis or the chipal compounds synthetic carrier of gel chromatography, affinity chromatography, and can be used for separating, identify, reclaiming precious metals such as inorganic metal ion and the uranium that from seawater, extracts, gold etc.The present invention makes full use of natural resource the abundantest, that can recover on this earth of Mierocrystalline cellulose, improves its added value.
4. the programmed cooling reversed phase suspension technique technology that cleans for preparing crosslinked spherical regenerated cellulose pearl body has following advantage: curing, regeneration, crosslinked three steps of cellulose bead body are integrated, simplified schedule of operation; Method is simple to operate, to equipment require lowly, be easy to realize industrialization, granularity and porosity can artificially be controlled; The regenerative process of cellulose bead body is not destroyed the spherical design and the pore structure of cellulose bead body.
More than the raw material of each step and the massfraction summation of prescription be 100%.
Description of drawings:
Fig. 1 is a kind of process flow sheet according to the preparation method of crosslinked spherical regenerated cellulose pearl body proposed by the invention.
Embodiment:
The present invention is described in detail below in conjunction with accompanying drawing:
Embodiment 1: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
(1) cellulosic dissolving
The raw material of present embodiment and prescription (unit-kilogram):
Linters: 1.0 kilograms
NMMOH
2The O:98 kilogram
Stablizer (Propylgallate and oxalic acid mixture, mass ratio 1: 9): 1.0 kilograms
Cellulose dissolution processing step and processing parameter: the paper pulp or the cotton of above-mentioned amount are put into the N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide that contains above-mentioned amount, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 85 ℃, solubilizing reaction 60min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 1.01%, add the stablizer of above-mentioned amount.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
The raw material of present embodiment and prescription (unit-kilogram):
The cellulose solution of above-mentioned steps (1): 30 kilograms
The 10%NMMO aqueous solution: 5 kilograms
Tensio-active agent (Span40, Tween 80 and oleic acid mixture, mass ratio 3: 1: 1): 1.9 kilograms
Dispersion agent (gelatin, polyvinyl alcohol and polyvinylpyrrolidone mixture, mass ratio 1: 1: 1): 1.1 kilograms
Low boiling point solvent (hexanaphthene): 59 kilograms
Activator (sodium hydroxide): 2.0 kilograms
Linking agent (epoxy chloropropane): 1.0 kilograms
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish the 10%NMMO aqueous solution that adds above-mentioned amount in the reactor of automatic feeding device of constant temperature system respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent, after stirring, the massfraction that slowly drips above-mentioned amount is Mierocrystalline cellulose-NMMO-aqueous solution of 1.01%, in 30min, dropwise, and rotating speed is controlled at 100r/min, temperature of reaction in the reinforced process is 75 ℃, after adding material temperature is controlled at 70 ℃, behind the reaction 45min, continue to be cooled to 60 ℃, behind the reaction 60min, cooling again, reduce to normal temperature, total is crosslinked always, be 210min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step carries out under 5 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 45 ℃, vacuum degree control reclaims low boiling point solvent at 0.05mPa, and the rate of recovery can reach 88%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 55 ℃, vacuum degree control is removed portion water at 0.1mPa, further after ultrafiltration and the ion-exchange, promptly gets N-methylmorpholine-N-oxide compound, its rate of recovery can reach 91.5%.This processing step can carry out under normal pressure.
Embodiment 2: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
(1) cellulosic dissolving
The raw material of present embodiment and prescription (unit-kilogram):
Absorbent cotton: 2.0 kilograms
NMMOH
2The O:96.5 kilogram
Stablizer (Propylgallate): 1.5 kilograms
Cellulose dissolution processing step and processing parameter: paper pulp or cotton are put into the N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide that contains above-mentioned amount, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 90 ℃, solubilizing reaction 75min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 2.03%, add 1.5 kilograms of stablizers.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
The raw material of present embodiment and prescription (unit-kilogram):
The cellulose solution of above-mentioned steps (1): 20 kilograms
The 10%NMMO aqueous solution: 10 kilograms
Tensio-active agent (oleic acid, Arlacelc and Span40 mixture, mass ratio 2: 7: 3): 1.5 kilograms
Dispersion agent (cellulose ethers): 1.5 kilograms
Low boiling point solvent (hexanaphthene): 63 kilograms
Activator (potassium hydroxide): 2.5 kilograms
Linking agent (acid of three isonitrile and epoxy chloropropionate alkylating mixture, mass ratio 2: 3): 1.5 kilograms
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish the 10%NMMO aqueous solution that adds above-mentioned amount in the reactor of automatic feeding device of constant temperature system respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent, after stirring, the massfraction that slowly drips above-mentioned amount is Mierocrystalline cellulose-NMMO-aqueous solution of 2.03%, in 45min, dropwise, and rotating speed is controlled at 250r/min, temperature of reaction in the reinforced process is 80 ℃, after adding material temperature is controlled at 75 ℃, behind the reaction 60min, continue to be cooled to 65 ℃, behind the reaction 60min, cooling again, reduce to normal temperature, total is crosslinked always, be 300min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step carries out under 3 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 40 ℃, vacuum degree control reclaims low boiling point solvent at 0.1mPa, and the rate of recovery can reach 90.5%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 60 ℃, vacuum degree control is removed portion water at 0.1mPa, after further filtration, ultrafiltration and the ion-exchange, promptly gets N-methylmorpholine-N-oxide compound, its rate of recovery can reach 93%.This processing step carries out under normal pressure.
Embodiment 3: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
(1) cellulosic dissolving
The raw material of present embodiment and prescription (unit-kilogram):
Deinked waste paper paper pulp: 3 kilograms
NMMOH
2The O:95.5 kilogram
Stablizer (saccharosonic acid, diethylamide and methylethyl ketoxime mixture, mass ratio 1: 2: 7): 1.5 kilograms
Cellulose dissolution processing step and processing parameter: paper pulp or cotton are put into the N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide that contains above-mentioned amount, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 85 ℃, solubilizing reaction 90min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 3.05%, add 1.5 kilograms of stablizers.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
The raw material of present embodiment and prescription (unit-kilogram):
The cellulose solution of above-mentioned steps (1): 20 kilograms
The 20%NMMO aqueous solution: 10 kilograms
Tensio-active agent (Span40, Span60 and Sodium dodecylbenzene sulfonate mixture, mass ratio 1: 1: 0.2): 2.5 kilograms
Dispersion agent (calcium phosphate powder, gelatin and polyvinyl alcohol mixture, mass ratio 1: 1: 9): 1.0 kilograms
Low boiling point solvent (isohexane): 61.5 kilograms
Activator (sodium hydroxide): 3.0 kilograms
Linking agent (formaldehyde and epoxy chloropropionate alkylating mixture, mass ratio 1: 11): 2.0 kilograms
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish the 20%NMMO aqueous solution that adds above-mentioned amount in the reactor of automatic feeding device of constant temperature system respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent, after stirring, the massfraction that slowly drips above-mentioned amount is Mierocrystalline cellulose-NMMO-aqueous solution of 3.05%, in 60min, dropwise, and rotating speed is controlled at 300r/min, temperature of reaction in the reinforced process is 65 ℃, after adding material temperature is controlled at 55 ℃, after the reaction 45, continue to be cooled to 60 ℃, after the reaction 30, cooling again, reduce to normal temperature, total is crosslinked always, be 360min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step carries out under 3 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 35 ℃, vacuum degree control reclaims low boiling point solvent at 0.1mPa, and the rate of recovery can reach 89%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 75 ℃, vacuum degree control is removed portion water at 0.05mPa, further filter and ion-exchange after, promptly get N-methylmorpholine-N-oxide compound, its rate of recovery can reach 90%.This processing step carries out under normal pressure.
Embodiment 4: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
(1) cellulosic dissolving
The raw material of present embodiment and prescription (unit-kilogram):
Pinus massoniana Lamb bleached pulp: 5.0 kilograms
NMMOH
2The O:93 kilogram
Stablizer (methylethyl ketoxime and composition thereof, mass ratio 1: 27): 2.0 kilograms
Cellulose dissolution processing step and processing parameter: paper pulp or cotton are put into the N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide that contains above-mentioned amount, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 95 ℃, solubilizing reaction 90min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 5.10%, add 2.0 kilograms stablizer.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
The raw material of present embodiment and prescription (unit-kilogram):
The cellulose solution of above-mentioned steps (1): 15 kilograms
The 30%NMMO aqueous solution: 5 kilograms
Tensio-active agent (oleic acid, Arlacelc and Span60 mixture, mass ratio 1: 1: 5): 3.0 kilograms
Dispersion agent (gelatin and Jian formula Tan Suan Magnesium mixture, mass ratio 1: 2): 1.0 kilograms
Low boiling point solvent (normal hexane): 70 kilograms
Activator (potassium hydroxide): 4.5
Linking agent (melamine formaldehyde (MF)): 1.5
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish the 30%NMMO aqueous solution that adds above-mentioned amount in the reactor of automatic feeding device of constant temperature system respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent etc., after stirring, the massfraction that slowly drips above-mentioned amount is Mierocrystalline cellulose-NMMO-aqueous solution of 5.10%, in 45min, dropwise, and rotating speed is controlled at 200r/min, temperature of reaction in the reinforced process is 75 ℃, after adding material temperature is controlled at 65 ℃, behind the reaction 75min, continue to be cooled to 45 ℃, behind the reaction 60min, cooling again, reduce to normal temperature, total is crosslinked always, be 240min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step carries out under 2.5 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 45 ℃, vacuum degree control reclaims low boiling point solvent at 0.1mPa, and the rate of recovery can reach 90%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 65 ℃, vacuum degree control is removed portion water at 0.1mPa, further after ultrafiltration and the ion-exchange, promptly gets N-methylmorpholine-N-oxide compound, its rate of recovery can reach 92.6%.This processing step carries out under normal pressure.
Embodiment 5: the processing step of present embodiment and order are as shown in Figure 1.
(1) cellulosic dissolving
The raw material of present embodiment and prescription (unit-kilogram):
Bamboo bleached pulp: 7.5 kilograms
NMMOH
2The O:89 kilogram
Stablizer (Propylgallate and sodium oxalate mixture, mass ratio 1: 5): 3.5 kilograms
Cellulose dissolution processing step and processing parameter: paper pulp or cotton are put into the N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide that contains above-mentioned amount, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 95 ℃, solubilizing reaction 120min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 7.77%, add 3.5 kilograms stablizer.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
The raw material of present embodiment and prescription (unit-kilogram):
The cellulose solution of above-mentioned steps (1): 10 kilograms
The 50%NMMO aqueous solution: 10 kilograms
Tensio-active agent (oleic acid, Span60 and sodium laurylsulfonate mixture, mass ratio 1: 5: 1): 1.5 kilograms
Dispersion agent (polyvinylpyrrolidone, phenolic aldehyde and urea aldehyde polycondensate, mass ratio 1: 1): 1.5 kilograms
Low boiling point solvent (97
#Gasoline): 74 kilograms
Activator (sodium hydroxide): 2.0 kilograms
Linking agent (epoxy chloropropane): 1.0 kilograms
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish the 50%NMMO aqueous solution that adds above-mentioned amount in the reactor of automatic feeding device of constant temperature system respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent, after stirring, the massfraction that slowly drips above-mentioned amount is Mierocrystalline cellulose-NMMO-aqueous solution of 7.77%, in 30min, dropwise, and rotating speed is controlled at 400r/min, temperature of reaction in the reinforced process is 55 ℃, after adding material temperature is controlled at 55 ℃, behind the reaction 60min, continue to be cooled to 45 ℃, behind the reaction 60min, cooling again, reduce to normal temperature, total is crosslinked always, be 300min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step carries out under 5 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 45 ℃, vacuum degree control reclaims low boiling point solvent at 0.1mPa, and the rate of recovery can reach 91%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 55 ℃, vacuum degree control is removed portion water at 0.1mPa, further filter and ion-exchange after, promptly get N-methylmorpholine-N-oxide compound, its rate of recovery can reach 87%.This processing step carries out under normal pressure.
Embodiment 6: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
(1) cellulosic dissolving
The raw material of present embodiment and prescription (unit-kilogram):
Reed bleached pulp: 4.0 kilograms
NMMOH
2The O:93 kilogram
Stablizer (Propylgallate and methylethyl ketoxime mixture, mass ratio 4: 1): 3.0 kilograms
Cellulose dissolution processing step and processing parameter: paper pulp or cotton are put into the N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide that contains above-mentioned amount, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 85 ℃, solubilizing reaction 90min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 4.12%, add 3.0 kilograms of stablizers.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
The raw material of present embodiment and prescription (unit-kilogram):
The cellulose solution of above-mentioned steps (1): 15 kilograms
The 30%NMMO aqueous solution: 18 kilograms
Tensio-active agent (Span80 and sodium laurylsulfonate mixture, mass ratio 12: 1): 2.0 kilograms
Dispersion agent (calcium phosphate powder, gelatin, polyvinyl alcohol mixture, mass ratio 1: 1: 4): 1.0 kilograms
Low boiling point solvent (kerosene): 63 kilograms
Activator (sodium hydroxide): 0.5 kilogram
Linking agent (succinic aldehyde and 1,3-two chloro-2-propanol mixture, mass ratio 1: 2): 0.5 kilogram
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish the 30%NMMO aqueous solution that adds above-mentioned amount in the reactor of automatic feeding device of constant temperature system respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent, after stirring, the massfraction that slowly drips above-mentioned amount is Mierocrystalline cellulose-NMMO-aqueous solution of 4.12%, in 60min, dropwise, and rotating speed is controlled at 300r/min, temperature of reaction in the reinforced process is 85 ℃, after adding material temperature is controlled at 85 ℃, behind the reaction 75min, continue to be cooled to 65 ℃, behind the reaction 60min, cooling again, reduce to normal temperature, total is crosslinked always, be 360min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step carries out under 7 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 35 ℃, vacuum degree control reclaims low boiling point solvent at 0.09mPa, and the rate of recovery can reach 86.8%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 75 ℃, vacuum degree control is removed portion water at 0.1mPa, after further filtration, ultrafiltration and the ion-exchange, promptly gets N-methylmorpholine-N-oxide compound, its rate of recovery can reach 95%.This processing step carries out under normal pressure.
Embodiment 7: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
(1) cellulosic dissolving
The raw material of present embodiment and prescription (unit-kilogram):
Reed bleached pulp: 7.0 kilograms
NMMOH
2The O:90 kilogram
Stablizer (sodium oxalate and oxalic acid mixture, mass ratio 1: 7): 3.0 kilograms
Cellulose dissolution processing step and processing parameter: the paper pulp or the cotton of above-mentioned amount are put into the N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide that contains above-mentioned amount, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 96 ℃, solubilizing reaction 90min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 7.22%, add the stablizer of above-mentioned amount.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
The raw material of present embodiment and prescription (unit-kilogram):
The cellulose solution of above-mentioned steps (1): 25 kilograms
The 50%NMMO aqueous solution: 10 kilograms
Tensio-active agent (Span80 and oleic acid mixture, mass ratio 6: 1): 1.9 kilograms
Dispersion agent (gelatin and polyvinylpyrrolidone mixture, mass ratio 1: 9): 1.1 kilograms
Low boiling point solvent (hexanaphthene): 58 kilograms
Activator (sodium hydroxide): 2.5 kilograms
Linking agent (epoxy chloropropane): 1.5 kilograms
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish the 50%NMMO aqueous solution that adds above-mentioned amount in the reactor of automatic feeding device of constant temperature system respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent, after stirring, the massfraction that slowly drips above-mentioned amount is Mierocrystalline cellulose-NMMO-aqueous solution of 7.22%, in 60min, dropwise, and rotating speed is controlled at 350r/min, temperature of reaction in the reinforced process is 85 ℃, after adding material temperature is controlled at 80 ℃, behind the reaction 60min, continue to be cooled to 60 ℃, behind the reaction 60min, cooling again, reduce to normal temperature, total is crosslinked always, be 300min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step carries out under 5 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 45 ℃, vacuum degree control reclaims low boiling point solvent at 0.08mPa, and the rate of recovery can reach 89.8%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 60 ℃, vacuum degree control is removed portion water at 0.1mPa, further after ultrafiltration and the ion-exchange, promptly gets N-methylmorpholine-N-oxide compound, its rate of recovery can reach 94%.This processing step can carry out under normal pressure.
Embodiment 8: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
(1) cellulosic dissolving
The raw material of present embodiment and prescription (unit-kilogram):
Disassociation old paper stock: 6.5 kilograms
NMMOH
2The O:92 kilogram
Stablizer (Propylgallate and oxalic acid mixture, mass ratio 1: 3): 1.5 kilograms
Cellulose dissolution processing step and processing parameter: the paper pulp or the cotton of above-mentioned amount are put into the N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide that contains above-mentioned amount, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 95 ℃, solubilizing reaction 105min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 6.60%, add the stablizer of above-mentioned amount.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
The raw material of present embodiment and prescription (unit-kilogram):
The cellulose solution of above-mentioned steps (1): 5 kilograms
The 10%NMMO aqueous solution: 21 kilograms
Tensio-active agent (Span40 and Tween 20 mixtures, mass ratio 8: 1): 2.0 kilograms
Dispersion agent (gelatin and polyvinyl alcohol mixture, mass ratio 1: 3): 1.0 kilograms
Low boiling point solvent (200
#Gasoline): 70 kilograms
Activator (potassium hydroxide): 0.8 kilogram
Linking agent (epoxy chloropropane): 0.2 kilogram
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish the 10%NMMO aqueous solution that adds above-mentioned amount in the reactor of automatic feeding device of constant temperature system respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent, after stirring, the massfraction that slowly drips above-mentioned amount is Mierocrystalline cellulose-NMMO-aqueous solution of 6.60%, in 30min, dropwise, and rotating speed is controlled at 100r/min, temperature of reaction in the reinforced process is 92 ℃, after adding material temperature is controlled at 87 ℃, behind the reaction 45min, continue to be cooled to 60 ℃, behind the reaction 60min, cooling again, reduce to normal temperature, total is crosslinked always, be 180min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step carries out under 9 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 45 ℃, vacuum degree control reclaims low boiling point solvent at 0.1mPa, and the rate of recovery can reach 90.5%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 75 ℃, vacuum degree control is removed portion water at 0.1mPa, further after ultrafiltration and the ion-exchange, promptly gets N-methylmorpholine-N-oxide compound, its rate of recovery can reach 94.7%.This processing step can carry out under normal pressure.
Embodiment 9: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
(1) cellulosic dissolving
The raw material of present embodiment and prescription (unit-kilogram):
Rice straw bleached pulp: 7.8 kilograms
NMMOH
2The O:91 kilogram
Stablizer (methylethyl ketoxime and composition thereof, mass ratio 18: 1): 1.2 kilograms
Cellulose dissolution processing step and processing parameter: the paper pulp or the cotton of above-mentioned amount are put into the N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide that contains above-mentioned amount, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 81 ℃, solubilizing reaction 90min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 7.90%, add the stablizer of above-mentioned amount.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
The raw material of present embodiment and prescription (unit-kilogram):
The cellulose solution of above-mentioned steps (1): 25 kilograms
The 5%NMMO aqueous solution: 2.5 kilograms
Tensio-active agent (Span40, sodium laurylsulfonate and oleic acid mixture, mass ratio 7: 1: 3): 2.9 kilograms
Dispersion agent (gelatin, polyvinyl alcohol and polyvinylpyrrolidone mixture, mass ratio 1: 1: 5): 1.1 kilograms
Low boiling point solvent (isohexane): 64.5 kilograms
Activator (sodium hydroxide): 2.0 kilograms
Linking agent (melamine formaldehyde (MF)): 2.0 kilograms
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish the 5%NMMO aqueous solution that adds above-mentioned amount in the reactor of automatic feeding device of constant temperature system respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent, after stirring, the massfraction that slowly drips above-mentioned amount is Mierocrystalline cellulose-NMMO-aqueous solution of 7.90%, in 47min, dropwise, and rotating speed is controlled at 280r/min, temperature of reaction in the reinforced process is 90 ℃, after adding material temperature is controlled at 82 ℃, behind the reaction 37min, continue to be cooled to 57 ℃, behind the reaction 60min, cooling again, reduce to normal temperature, total is crosslinked always, be 270min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step carries out under 1.5 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 35 ℃, vacuum degree control reclaims low boiling point solvent at 0.05mPa, and the rate of recovery can reach 82%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 70 ℃, vacuum degree control is removed portion water at 0.1mPa, further filter and ion-exchange after, promptly get N-methylmorpholine-N-oxide compound, its rate of recovery can reach 92.7%.This processing step can carry out under normal pressure.
Embodiment 10: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
(1) cellulosic dissolving
The raw material of present embodiment and prescription (unit-kilogram):
Bamboo bleached pulp: 3.5 kilograms
NMMOH
2The O:95 kilogram
Stablizer (sodium oxalate and diethylamide mixture, mass ratio 1: 5): 1.5 kilograms
Cellulose dissolution processing step and processing parameter: the paper pulp or the cotton of above-mentioned amount are put into the N-methylmorpholine-N-oxide compound (N-methylmorpholine-N-oxide that contains above-mentioned amount, abbreviation NMMO) in the reactor of the aqueous solution, temperature of reaction is controlled at 86 ℃, solubilizing reaction 145min, after forming massfraction and be Mierocrystalline cellulose-NMMO-aqueous solution of 3.55%, add the stablizer of above-mentioned amount.This processing step carries out under normal pressure.
(2) programmed cooling anti-phase suspension
The raw material of present embodiment and prescription (unit-kilogram):
The cellulose solution of above-mentioned steps (1): 10 kilograms
The 35%NMMO aqueous solution: 10 kilograms
Tensio-active agent (Span40, Tween 80 and Arlacelc mixture, mass ratio 10: 1: 2): 1.5 kilograms
Dispersion agent (calcium phosphate powder and polyvinylpyrrolidone mixture, mass ratio 3: 7): 1.0 kilograms
Low boiling point solvent (hexanaphthene): 74.5 kilograms
Activator (potassium hydroxide): 2.0 kilograms
Linking agent (epoxy chloropropane): 1.0 kilograms
Programmed cooling anti-phase suspension processing step and processing parameter: be equipped with condensation reflux unit and in establish the 35%NMMO aqueous solution that adds above-mentioned amount in the reactor of automatic feeding device of constant temperature system respectively, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent, after stirring, the massfraction that slowly drips above-mentioned amount is Mierocrystalline cellulose-NMMO-aqueous solution of 3.55%, in 35min, dropwise, and rotating speed is controlled at 100r/min, temperature of reaction in the reinforced process is 65 ℃, after adding material temperature is controlled at 60 ℃, behind the reaction 45min, continue to be cooled to 55 ℃, behind the reaction 60min, cooling again, reduce to normal temperature, total is crosslinked always, be 360min set time, can obtain the crosslinked spherical regenerated cellulose pearl body of different-grain diameter.This processing step carries out under 1 normal atmosphere.
(3) recovery of solvent
After utilizing filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 42 ℃, vacuum degree control reclaims low boiling point solvent at 0.06mPa, and the rate of recovery can reach 86.1%; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 56 ℃, vacuum degree control is removed portion water at 0.1mPa, after further filtration, ultrafiltration and the ion-exchange, promptly gets N-methylmorpholine-N-oxide compound, its rate of recovery can reach 87.9%.This processing step can carry out under normal pressure.
Some physico-chemical properties of the crosslinked spherical regenerated cellulose pearl body that the foregoing description makes see Table 1 to table 5:
The particle diameter of table 1 cellulose bead body and the relation of cell size and specific surface area
| Pearl body particle diameter (μ m) | 1-10 | 10-40 | 40-80 | 80-120 | 120-200 |
| Cell size (%) | 92.6-95.1 | 89.8-92.0 | 86.7-89.0 | 83.1-86.2 | 80.8-83.0 |
| Specific surface area (m 2/g) | 590±70 | 482±40 | 378±60 | 280±35 | 172.0±50 |
The acidproof ability of table 2 cellulose bead body
| Acid concentration (mol/L) | 0.5 | 1.0 | 2.0 | 4.0 | 6.0 |
| The volumetric expansion degree | 1.52 | 1.63 | 1.87 | 2.01 | 2.26 |
| Mass loss (%) | 0.49 | 0.98 | 2.01 | 5.59 | 12.95 |
Annotate: the cellulose bead body that with the particle diameter is 40-80 μ m is a research object, and dwell temperature is 20 ℃, and time of repose is 24h.
The alkaline-resisting ability of table 3 cellulose bead body
| Alkali concn (mol/L) | 0.5 | 1.0 | 2.0 | 4.0 | 6.0 |
| The volumetric expansion degree | 2.45 | 3.03 | 4.89 | 6.07 | 4.92 |
| Mass loss (%) | 1.78 | 5.16 | 11.52 | 14.72 | 20.29 |
Annotate: the cellulose bead body that with the particle diameter is 40-80 μ m is a research object, and dwell temperature is 20 ℃, and time of repose is 24h.
The resistance of oxidation of table 4 cellulose bead body
| Oxidization time (h) | 6.0 | 12.0 | 24.0 | 36.0 | 48.0 | 96.0 |
| Mass loss (%) | 0.06 | 0.07 | 0.12 | 0.14 | 0.18 | 0.20 |
Annotate: the cellulose bead body that with the particle diameter is 40-80 μ m is a research object, and oxidizing temperature is 65 ℃, and oxygenant is 3.0%H
2O
2With 1m 0.12%FeSO
4
The antibiont degradation capability of table 5 cellulose bead body
| Degradation time (d) | 10 | 30 | 60 | 90 | 120 | 150 |
| Mass loss (%) | 0.15 | 0.36 | 0.72 | 1.68 | 3.59 | 4.73 |
Annotate: the cellulose bead body that with the particle diameter is 40-80 μ m is a research object, and degradation temperature is 20 ℃.
Claims (13)
1. crosslinked spherical regenerated cellulose pearl body, adopt direct dissolving cellulos to make cellulose solution, directly prepare crosslinked spherical regenerated cellulose pearl body with the programmed cooling reversed phase suspension technique then, the particle size distribution range that it is characterized in that described crosslinked spherical regenerated cellulose pearl body is respectively 1～10 μ m, 10～40 μ m, 40～80 μ m, 80～120 μ m, 120～200 μ m, mean pore size is 5～30nm, and specific surface area is 120～650m
2/ g, water ratio 50%～75%, skeletal density 0.91～1.30g/ml, apparent density 0.45～0.81g/ml, pore volume 0.15～1.12ml/g, cell size 80%～96%.
2. the production method of the described crosslinked spherical regenerated cellulose of claim 1 pearl body, comprise the steps: (1) cellulosic dissolving step in regular turn: paper pulp or the cotton temperature with 80～100 ℃ is dissolved in the aqueous solution of N-methylmorpholine-N-oxide compound, and it is Mierocrystalline cellulose-NMMO solution of 0.1%～8.0% that normal pressure forms massfraction down; (2) programmed cooling anti-phase suspension step: Mierocrystalline cellulose-NMMO-aqueous solution is scattered in the not miscible medium, and the mode by external force effect and programmed cooling prepares crosslinked spherical regenerated cellulose pearl body under 1 to 10 normal atmosphere; Wherein, dispersion medium is made up of 1.0%～50%NMMO aqueous solution, tensio-active agent, dispersion agent, low boiling point solvent, activator and linking agent, and be 120～360min set time.
3. the production method of crosslinked spherical regenerated cellulose pearl body according to claim 2 is characterized in that:
(1) cellulosic dissolved raw material and prescription are in massfraction:
Raw material and prescription (massfraction):
Paper pulp or cotton: 0.1～8%
NMMO·H
2O：87～99％
Stablizer: 0.1～5%
(2) raw material of programmed cooling anti-phase suspension step and prescription are in massfraction:
The cellulose solution of step (1): 1.0～32%
The 1.0%-50%NMMO aqueous solution: 1.0～30%
Tensio-active agent: 0.1～5.0%
Dispersion agent: 0.1%～1.5%
Low boiling point solvent: 30～75%
Activator: 0.1～5.0%
Linking agent: 0.1～5.0%
4. according to the preparation method of claim 2 or 3 described crosslinked spherical regenerated cellulose pearl bodies, after it is characterized in that utilizing under the normal pressure filtration and sieve method with crosslinked spherical regenerated cellulose pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize vacuum distillation apparatus then, temperature is controlled at 25～45 ℃, vacuum degree control reclaims low boiling point solvent at 0.05～0.1mPa; Then with surplus solution with hydrogen peroxide oxidation after, temperature is controlled at 55～75 ℃, vacuum degree control is removed portion water at 0.05～0.1mPa, further after filtration under the normal pressure, ultrafiltration or the ion-exchange, promptly gets N-methylmorpholine-N-oxide compound.
5. according to the preparation method of claim 2 or 3 described crosslinked spherical regenerated cellulose pearl bodies, it is characterized in that external force effect employing stirring, stirring velocity is 20-400r/min.
6. according to the preparation method of claim 2 or 3 described crosslinked spherical regenerated cellulose pearl bodies, it is characterized in that it is that raw material is made by sulphate process, sulphite process or alkaline process and through the paper pulp behind chemistry or the bio-bleaching, deinked waste paper paper pulp, disassociation old paper stock, cotton is selected from common cotton, linters, absorbent cotton that used paper pulp is selected from bagasse, Pinus massoniana Lamb, bamboo, rice straw, reed material.
7. according to the preparation method of claim 2 or 3 described crosslinked spherical regenerated cellulose pearl bodies, it is characterized in that the solvent that uses is N-methylmorpholine-N-oxide compound, water ratio is 4～50%.
8. according to the preparation method of claim 2 or 3 described crosslinked spherical regenerated cellulose pearl bodies, it is characterized in that the stablizer that uses has a kind of Propylgallate, oxalic acid, sodium oxalate, potassium oxalate, saccharosonic acid, diethylamide, methylethyl ketoxime and composition thereof of being selected from least, add-on is 0.1～5%.
9. according to the preparation method of claim 2 or 3 described crosslinked spherical regenerated cellulose pearl bodies, it is characterized in that employed solvent is the N-methylmorpholine-N-oxide water solution of different concns and the mixture of other low boiling point solvent in the dispersion medium.The concentration of N-methylmorpholine-N-oxide water solution is 1.0%～50%; Low boiling point solvent has a kind of hexanaphthene, isohexane, normal hexane, 97 of being selected from least
#Gasoline, 200
#Gasoline, kerosene.
10. according to the preparation method of claim 2 or 3 described crosslinked spherical regenerated cellulose pearl bodies, it is characterized in that the tensio-active agent that uses has a kind of oleic acid, Arlacelc, Arlace160, Span20, Span40, Span60, Span80, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, Tween20, Tween40, Tween60, Tween80, sulfonated castor oil of being selected from least, add-on is 0.1～5.0%.
11., it is characterized in that it is 0.1%～1.5% that the dispersion agent that uses has a kind of Jian of being selected from formula Tan Suan Magnesium, calcium phosphate powder, gelatin, polyvinyl alcohol, acid polyethylene, polyvinylpyrrolidone, phenolic aldehyde and urea aldehyde polycondensate and cellulose ethers add-on at least according to the preparation method of claim 2 or 3 described crosslinked spherical regenerated cellulose pearl bodies.
12. according to the preparation method of claim 2 or 3 described crosslinked spherical regenerated cellulose pearl bodies, it is characterized in that the activator that uses has a kind of sodium hydroxide, potassium hydroxide of being selected from least, add-on is 0.1～5.0%.
13. preparation method according to claim 2 or 3 described crosslinked spherical regenerated cellulose pearl bodies, it is characterized in that linking agent has a kind of formaldehyde, propenal, succinic aldehyde, melamine formaldehyde (MF), epoxy chloropropane, 1 of being selected from least, 3-two chloro-2-propyl alcohol, three isonitrile acid, add-on is 0.1～5.0%.
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| CN101357325B (en) * | 2008-09-18 | 2012-05-23 | 福州大学 | Globular cellulose chelate sorbent containing amidoxime group and carboxy and preparation method thereof |
| CN101906214A (en) * | 2009-06-05 | 2010-12-08 | 华东理工大学 | Method for preparing crosslinked spherical cellulose particles |
| CN109201020A (en) * | 2018-11-17 | 2019-01-15 | 管敏富 | A kind of preparation method of cellulose microsphere adsorbent |
| CN109939657B (en) * | 2019-03-28 | 2022-03-04 | 广东工业大学 | Macroporous phenolic resin, preparation method thereof and application thereof in adsorption of 5-hydroxymethylfurfural |
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