CN104177642A - Expanded bed adsorption matrix and preparation method thereof - Google Patents
Expanded bed adsorption matrix and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an expanded bed adsorption matrix and a preparation method thereof. The preparation method comprises the following steps: 1) dissolving acrylamide, a crosslinking agent and a water-soluble gelatinized starch colloid liquid in deionized water; 2) adding inorganic weighting agent particles into the mixed solution, and uniformly dispersing; 3) adding an initiator into the uniformly dispersed solution, adding the solution into a dispersing-agent-dissolved continuous phase (oil phase) to constitute a reversed phase suspension disperse system; 4) heating the reversed phase suspension disperse system to carry out polymerization reaction; 5) after the reaction is finished, removing the continuous phase, cleaning, and adding amylase to remove the water-soluble starch, thereby obtaining composite microspheres; and 6) filtering the composite microspheres, washing, and carrying out wet screening to finally obtain the expanded bed matrix using polyacrylamide as the base material. The expanded bed matrix has the advantages of favorable sphericity, higher density, larger pore size, reasonable particle size distribution, favorable mechanical strength, favorable biocompatibility, stable properties, low cost and the like.
Description
Technical field
The present invention relates to ExPANDED BED ADSORPTION TECHNIQUE field, relate in particular to a kind of Matrices for Expanded Bed Adsorption and preparation method thereof.
Background technology
ExPANDED BED ADSORPTION TECHNIQUE is a kind of integrated separation technology, collects the concentrated and initial stage purifying of solid-liquid separation, enrichment in a unit operation, directly target acquisition product from fermented liquid or cell homogenates.The Matrices for Expanded Bed Adsorption of excellent property is the key of Expanded Bed Adsorption, directly affects mass transfer and the separation efficiency of sepn process.For Matrices for Expanded Bed Adsorption, need to carry out special design, include the grain diameter of reasonable layout, the pellet density of reasonable layout, the flow velocity of Expanded Bed Adsorption process is higher simultaneously, also needs matrix to have larger aperture, is convenient to material transfer.
At present the basic raw material commercially available and Matrices for Expanded Bed Adsorption reported is mainly agarose, dextran and Mierocrystalline cellulose, has no to take the Matrices for Expanded Bed Adsorption that polyacrylamide is basic raw material.Acrylamide is a kind of conventional chemical feedstocks, wide material sources, low price.The advantages such as polyacrylamide microsphere has good hydrophilic property, good at pH1-10 scope internal stability, hole link is good, good springiness, restorability are strong, and be not biological degradation, there is certain physical strength, receive much concern in recent years.On market, there is the multiple fixed bed chromatography medium that polyacrylamide is basic material of take, for fields such as bioseparation, blood purification, immunodiagnosis and medicament slow releases.But so far there are no, make the report of Expanded Bed Adsorption medium, more without commodity medium, when its major cause is to realize acrylamide monomer polymerization balling-up, weighting agent embedding wherein, be difficult to obtain particle diameter and the suitable microballoon of density, in addition inner duct is less, therefore cannot reach the requirement of Matrices for Expanded Bed Adsorption.
Via Inverse-Phase Suspension Polymerization is the most general method of preparing Matrices for Expanded Bed Adsorption.In polypropylene amides gel micro-ball forming process, to be polymerized under the effect of linking agent and initiator by acrylamide monomer, therefore in order to improve the density of polypropylene amides gel micro-ball, must in acrylamide soln, add weighting agent, but because the viscosity of acrylamide solution is lower, be difficult to when polymerization weighting agent embedding wherein, the larger weighting agent of density especially, as stainless steel, wolfram varbide etc.This problem never obtains fine solution, has also directly affected to take polyacrylamide and prepare the research of Matrices for Expanded Bed Adsorption as basic material.
The invention discloses a kind of method and solve the difficulty that via Inverse-Phase Suspension Polymerization is prepared polyacrylamide Matrices for Expanded Bed Adsorption: select pasted starch as the additive of acrylamide polymerization process, this pasted starch is a kind of good thickening material, is also a kind of effective pore-creating agent simultaneously.After adding pasted starch, the viscosity of acrylamide solution improves greatly, can be well comprising that (density reaches 15.6g/cm to wolfram varbide when inverse suspension polymerization
3) etc. various weighting agents be wrapping in polypropylene amides gel micro-ball, realized the object that increases polypropylene amides gel micro-ball density, adopt α-amylase after pasted starch hydrolysis simultaneously, make to have stayed in microballoon larger aperture, form good pore size distribution, met the requirement of Matrices for Expanded Bed Adsorption completely.This interpolation pasted starch, as the method for pore-creating agent and thickening material, has played the dual function of reaming and increase water viscosity, thereby the weighting agent that density is larger can be embedded in polyacrylamide microsphere preferably, realizes settling at one go of reaming and weightening finish.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, and it is Matrices for Expanded Bed Adsorption of basic material, reaming and preparation method thereof that a kind of polyacrylamide is provided.
Technical scheme of the present invention is as follows:
The preparation method of Matrices for Expanded Bed Adsorption comprises the steps:
1) monomer acrylamide and linking agent being mixed with to total mass concentration by the mixed in molar ratio of 40:1～30:1 is 20%～50% solution;
2) starch is joined in deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous, i.e. gelatinization of starch solution, and the mass concentration of gelatinization of starch solution is 5%～10%; Gelatinization of starch solution is joined to step 1) in acrylamide/cross-linking agent solution of preparing, the mass ratio that makes gelatinization of starch solution and acrylamide/cross-linking agent solution is 1:10～5:10; Add weighting agent particle, the mass ratio 0.1～1.3:1 of weighting agent particle and acrylamide/cross-linking agent solution, mixes and stirs, and under 20～35 ℃ of conditions, carries out ultrasonic dispersion, and weighting agent uniform particles is dispersed in solution;
3) under 0～5 ℃ of condition, initiator being joined to step 2) in the solution that obtains, the mass ratio of initiator and acrylamide is 2:100～5:100, stirs and becomes the disperse phase of preparation matrix; Disperse phase joins in the external phase that is dissolved with dispersion agent, and disperse phase and external phase mass ratio are 1:2～1:5, and dispersion agent is sorbester p17, and the mass percent in external phase is 2.5%～4%; At mechanical stirring rotating speed, be under 350～550rpm, stir 3～5min, form anti-phase suspension dispersion system;
4), under the condition that is 350～550rpm at mixing speed, above-mentioned anti-phase suspension dispersion system is heated in water bath with thermostatic control, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 30～60 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, remove the external phase in anti-phase suspension dispersion system, with deionized water rinsing, then the α-amylase solution that adds 1～2 times of volume, the massfraction of α-amylase solution is 0.5%～1.5%, system is at room temperature placed in to 100rpm～300rpm shaking table complete to starch degradation, 4～5 washings of moisture with 5～10 times of volumes, and room temperature is flooded in 20%～30% (v/v) acetum, with the moisture of 5～10 times of volumes, wash for 4～5 times again, hygrometric state screening, obtain the polyacrylamide microsphere of macropore, this microballoon is Matrices for Expanded Bed Adsorption.
Described water soluble starch is commercially available wheat starch, tapioca (flour) or sweet potato starch; Weighting agent is titanium dioxide granule, stainless steel particle, nickel powder or tungsten carbide particle; Linking agent is N, N '-methylene-bisacrylamide; Initiator is ammonium persulphate; Dispersion agent is sorbester p17; External phase is the mixture of hexanaphthene and edible oil, and the mass ratio of hexanaphthene and edible oil is 1:1～1:5.
The polymer network skeleton of Matrices for Expanded Bed Adsorption prepared by described preparation method is polyacrylamide, and weighting agent is embedded in polymer network skeleton, and the size distribution of Matrices for Expanded Bed Adsorption is 100～300 μ m, and density is 1.02～1.40g/cm
3, mean porosities is 75%～92%, aperture is 0.5～1.2 μ m.
The marked improvement that the present invention compared with prior art has:
1) the novel expanded bed adsorbing base of preparing meets the requirement of Matrices for Expanded Bed Adsorption density distribution and size distribution, can make to expand the stable expansion of bed, by regulating the add-on of weighting agent, the density of adjustable Matrices for Expanded Bed Adsorption, to adapt to different operation flow velocitys simultaneously.
2) the well-regulated spherical design of novel expanded bed adsorbing base tool of preparing can obtain good hydrodynamics in expanding bed.
3) the novel expanded bed adsorbing base of preparing has larger density, controlled aperture and pore size distribution, physical strength preferably, can adapt to the mass transfer requirement under high flow rate in expanding bed.
4) the novel expanded bed adsorbing base stable chemical nature of preparing can be reused in different moving phase, and can carry out derivatize by the mode of direct modification or interpolation function monomer, obtains having the adsorption medium of difference in functionality group.
5) the novel expanded bed adsorbing base of preparing has good biocompatibility, can be used as the matrix of the separation and purification of various biologically active substances.
6) preparation technology is simple, easily controls and amplifies, with low cost.
Accompanying drawing explanation
Fig. 1 is the microphotograph of Matrices for Expanded Bed Adsorption outward appearance in the embodiment of the present invention 3;
Fig. 2 is the electron micrograph of Matrices for Expanded Bed Adsorption outward appearance in the embodiment of the present invention 3;
Fig. 3 is the pore texture figure on Matrices for Expanded Bed Adsorption surface in the embodiment of the present invention 3;
Fig. 4 is the size distribution figure of Matrices for Expanded Bed Adsorption in the embodiment of the present invention 3.
Embodiment
The preparation method of Matrices for Expanded Bed Adsorption comprises the steps:
1) monomer acrylamide and linking agent being mixed with to total mass concentration by the mixed in molar ratio of 40:1～30:1 is 20%～50% solution;
2) starch is joined in deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous, i.e. gelatinization of starch solution, and the mass concentration of gelatinization of starch solution is 5%～10%; Gelatinization of starch solution is joined to step 1) in acrylamide/cross-linking agent solution of preparing, the mass ratio that makes gelatinization of starch solution and acrylamide/cross-linking agent solution is 1:10～5:10; Add weighting agent particle, the mass ratio 0.1～1.3:1 of weighting agent particle and acrylamide/cross-linking agent solution, mixes and stirs, and under 20～35 ℃ of conditions, carries out ultrasonic dispersion, and weighting agent uniform particles is dispersed in solution;
3) under 0～5 ℃ of condition, initiator being joined to step 2) in the solution that obtains, the mass ratio of initiator and acrylamide is 2:100～5:100, stirs and becomes the disperse phase of preparation matrix; Disperse phase joins in the external phase that is dissolved with dispersion agent, and disperse phase and external phase mass ratio are 1:2～1:5, and dispersion agent is sorbester p17, and the mass percent in external phase is 2.5%～4%; At mechanical stirring rotating speed, be under 350～550rpm, stir 3～5min, form anti-phase suspension dispersion system;
4), under the condition that is 350～550rpm at mixing speed, above-mentioned anti-phase suspension dispersion system is heated in water bath with thermostatic control, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 30～60 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, remove the external phase in anti-phase suspension dispersion system, with deionized water rinsing, then the α-amylase solution that adds 1～2 times of volume, the massfraction of α-amylase solution is 0.5%～1.5%, system is at room temperature placed in to 100rpm～300rpm shaking table complete to starch degradation, 4～5 washings of moisture with 5～10 times of volumes, and room temperature is flooded in 20%～30% (v/v) acetum, with the moisture of 5～10 times of volumes, wash for 4～5 times again, hygrometric state screening, obtain the polyacrylamide microsphere of macropore, this microballoon is Matrices for Expanded Bed Adsorption.
Described water soluble starch is commercially available wheat starch, tapioca (flour) or sweet potato starch; Weighting agent is titanium dioxide granule, stainless steel particle, nickel powder or tungsten carbide particle; Linking agent is N, N '-methylene-bisacrylamide; Initiator is ammonium persulphate; Dispersion agent is sorbester p17; External phase is the mixture of hexanaphthene and edible oil, and the mass ratio of hexanaphthene and edible oil is 1:1～1:5.
The polymer network skeleton of Matrices for Expanded Bed Adsorption prepared by described preparation method is polyacrylamide, and weighting agent is embedded in polymer network skeleton, and the size distribution of Matrices for Expanded Bed Adsorption is 100～300 μ m, and density is 1.02～1.40g/cm
3, mean porosities is 75%～92%, aperture is 0.5～1.2 μ m.
The present invention is further illustrated by the following examples, and the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited only to this.
Embodiment 1
1), by acrylamide and linking agent N, it is 20% solution that N '-methylene-bisacrylamide is mixed with total mass concentration by the mixed in molar ratio of 40:1;
2) sweet potato starch is joined in deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous, and the mass concentration of gelatinization of starch solution is 5%; Gelatinization of starch solution is joined in the acrylamide/cross-linking agent solution having prepared, the mass ratio of starch solution and acrylamide/cross-linking agent solution is 1:10; Add weighting agent titanium dioxide granule, the mass ratio 1:5 of weighting agent particle and acrylamide/cross-linking agent solution, mixes and stirs, and under 20 ℃ of conditions, carries out ultrasonic dispersion, and weighting agent uniform particles is dispersed in solution;
3) under 0 ℃ of condition, initiator ammonium persulfate is joined in scattered solution, ammonium persulphate and the proportion of acylamide are 2:100, stirring and dissolving is as disperse phase, disperse phase joins in the external phase of hexanaphthene and edible oil mixing solutions composition, the mass ratio of hexanaphthene and edible oil is 1:1, contain mass percent and be 2.5% sorbester p17, disperse phase and external phase mass ratio are 1:2, under the condition that is 350rpm at mechanical stirring rotating speed, form anti-phase suspension dispersion system, and stir 3min;
4), under the condition that is 350rpm at mixing speed, with water bath with thermostatic control, heat above-mentioned dispersion system, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 30 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, removes the external phase in anti-phase suspension dispersion system, with after deionized water rinsing, the α-amylase solution that adds 1 times of volume, the massfraction of α-amylase solution is 0.5%, system is placed in to 100rpm shaking table at normal temperatures complete to starch degradation, with 4 washings of moisture of 5 times of volumes, and room temperature is flooded in 20% (v/v) acetum, with 4 washings of moisture of 5 times of volumes, hygrometric state screening, obtains polyacrylamide microsphere again.Microballoon density is 1.02-1.11g/cm
3, size distribution is 100-285 μ m, and mean porosities is 85.6%, and pore size distribution is 0.5～1.0 μ m, and this microballoon can be used as a kind of Matrices for Expanded Bed Adsorption.
Embodiment 2
1), by acrylamide and linking agent N, it is 50% solution that N '-methylene-bisacrylamide is mixed with total mass concentration by the mixed in molar ratio of 30:1;
2) tapioca (flour) is joined in deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous, and the mass concentration of gelatinization of starch solution is 10%; Starch solution after gelatinization is joined in the acrylamide/cross-linking agent solution having prepared, the mass ratio of starch solution and acrylamide/cross-linking agent solution is 5:10; Add weighting agent tungsten carbide particle, the mass ratio 1.3:1 of weighting agent particle and acrylamide/cross-linking agent solution, mixes and stirs, and under 35 ℃ of conditions, carries out ultrasonic dispersion, and weighting agent uniform particles is dispersed in solution;
3) under 5 ℃ of conditions, initiator ammonium persulfate is joined in scattered solution, ammonium persulphate and the proportion of acylamide are 5:100, and stirring and dissolving is as disperse phase, and disperse phase joins in the external phase of hexanaphthene and edible oil mixing solutions composition, the mass ratio of hexanaphthene and edible oil is 1:5, contain mass percent and be 4% sorbester p17, disperse phase and external phase mass ratio are 1:5, under the condition that is 550rpm at mechanical stirring rotating speed, form anti-phase suspension dispersion system, and stir 5min;
4), under the condition that is 550rpm at mixing speed, with water bath with thermostatic control, heat above-mentioned dispersion system, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 60 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, remove the external phase in anti-phase suspension dispersion system, with after deionized water rinsing, the α-amylase solution that adds 2 times of volumes, the massfraction of α-amylase solution is 1.5%, system is placed in to 300rpm shaking table at normal temperatures complete to starch degradation, 5 washings of moisture with 10 times of volumes, and room temperature is flooded in 30% (v/v) acetum, with 5 washings of moisture of 10 times of volumes, hygrometric state screening, obtains polyacrylamide reaming microballoon again.Microballoon density is 1.15-1.40g/cm3, and size distribution is 102-300 μ m, and mean porosities is 82.5%, and pore size distribution is 0.7～1.2 μ m, and this microballoon can be used as a kind of novel expansion bed substrate.
Embodiment 3
1), by 3g acrylamide and 0.17g linking agent N, N '-methylene-bisacrylamide joins and in 15mL deionized water, is hybridly prepared into total mass concentration is 21% solution;
2) 1g wheat starch is joined in 15mL deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous; 5g gelatinization of starch solution and 2g weighting agent tungsten carbide particle are joined in acrylamide/linking agent mixing solutions, mix and stir, under 20 ℃ of conditions, carry out ultrasonic dispersion, weighting agent uniform particles is dispersed in solution;
3) under 5 ℃ of conditions, using 0.15g initiator ammonium persulfate join in scattered solution and stirring and dissolving as disperse phase, disperse phase joins in the 15g hexanaphthene and 30g edible oil external phase that is dissolved with 1.2g sorbester p17, under the condition that is 350rpm at mechanical stirring rotating speed, form anti-phase suspension dispersion system, and stir 3min;
4), under the condition that is 350rpm at mixing speed, with water bath with thermostatic control, heat above-mentioned dispersion system, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 60 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, remove the external phase in anti-phase suspension dispersion system, with after deionized water rinsing, add 100mL to contain in 1% α-amylase solution except destarching, system is placed in to 180rpm shaking table at normal temperatures complete to starch degradation, with 5 washings of moisture of 10 times of volumes, and room temperature is flooded in 25% (v/v) acetum, then washs for 5 times with the moisture of 10 times of volumes, hygrometric state screening, obtains polyacrylamide reaming microballoon.Microballoon density is 1.15-1.28g/cm
3, size distribution is 100-300 μ m, and mean porosities is 83.4%, and pore size distribution is 0.7～1.2 μ m, and this microballoon can be used as a kind of novel expansion bed substrate.
Embodiment 4
1), by 3g acrylamide and 0.17g linking agent N, N '-methylene-bisacrylamide joins and in 15mL deionized water, is hybridly prepared into total mass concentration is 21% solution;
2) 1g wheat starch is joined in 15mL deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous; 5g gelatinization of starch solution and 2g weighting agent nano silicon carbide tungsten particle, join in acrylamide/linking agent mixing solutions, mix and stir, under 20 ℃ of conditions, carry out ultrasonic dispersion, weighting agent uniform particles is dispersed in solution;
3) under 5 ℃ of conditions, using 0.15g initiator ammonium persulfate join in scattered solution and stirring and dissolving as disperse phase, disperse phase joins in the 15g hexanaphthene and 30g edible oil external phase that is dissolved with 1.2g sorbester p17, under the condition that is 350rpm at mechanical stirring rotating speed, form anti-phase suspension dispersion system, and stir 3min;
4), under the condition that is 350rpm at mixing speed, with water bath with thermostatic control, heat above-mentioned dispersion system, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 40 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, remove the external phase in anti-phase suspension dispersion system, with after deionized water rinsing, add 80mL to contain in 0.5% α-amylase solution except destarching, system is placed in to 120rpm shaking table at normal temperatures complete to starch degradation, with 4 washings of moisture of 5 times of volumes, and room temperature is flooded in 20% (v/v) acetum, then washs for 4 times with the moisture of 5 times of volumes, hygrometric state screening, obtains polyacrylamide reaming microballoon.Microballoon density is 1.15-1.31g/cm3, and size distribution is 105-285 μ m, and mean porosities is 92.0%, and pore size distribution is 0.6～1.1 μ m, and this microballoon can be used as a kind of novel expansion bed substrate.
Embodiment 5
1), by 7.1g acrylamide and 0.5g linking agent N, N '-methylene-bisacrylamide joins and in 15mL deionized water, is hybridly prepared into total mass concentration is 50% solution;
2) 1g tapioca (flour) is joined in 15mL deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous; 5g gelatinization of starch solution and 2g weighting agent stainless steel particle, join in acrylamide/linking agent mixing solutions, mix and stir, under 25 ℃ of conditions, carry out ultrasonic dispersion, weighting agent uniform particles is dispersed in solution;
3) under 0 ℃ of condition, using 0.15g initiator ammonium persulfate join in scattered solution and stirring and dissolving as disperse phase, disperse phase joins in the 20g hexanaphthene and 40g edible oil external phase that is dissolved with 1.8g sorbester p17, under the condition that is 450rpm at mechanical stirring rotating speed, form anti-phase suspension dispersion system, and stir 5min;
4), under the condition that is 450rpm at mixing speed, with water bath with thermostatic control, heat above-mentioned dispersion system, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 50 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, remove the external phase in anti-phase suspension dispersion system, with after deionized water rinsing, add 100mL to contain in 1% amylase solution except destarching, system is placed in to 180rpm shaking table at normal temperatures complete to starch degradation, with 4 washings of moisture of 8 times of volumes, and room temperature is flooded in 25% (v/v) acetum, then washs for 4 times with the moisture of 8 times of volumes, hygrometric state screening, obtains polyacrylamide reaming microballoon.Microballoon density is 1.13-1.23g/cm3, and size distribution is 100-290 μ m, and mean porosities is 80.3%, and pore size distribution is 0.5～1.2 μ m, and this microballoon can be used as a kind of novel expansion bed substrate.
Embodiment 6
1), by 7.1g acrylamide and 0.5g linking agent N, N '-methylene-bisacrylamide joins and in 15mL deionized water, is hybridly prepared into total mass concentration is 50% solution;
2) 1g sweet potato starch is joined in 15mL deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous; 5g gelatinization of starch solution and 9g weighting agent nano silicon carbide tungsten particle, join in acrylamide/linking agent mixing solutions, mix and stir, under 25 ℃ of conditions, carry out ultrasonic dispersion, weighting agent uniform particles is dispersed in solution;
3) under 0 ℃ of condition, using 0.15g initiator ammonium persulfate join in scattered solution and stirring and dissolving as disperse phase, disperse phase joins in the 25g hexanaphthene and 50g edible oil external phase that is dissolved with 3g sorbester p17, under the condition that is 550rpm at mechanical stirring rotating speed, form anti-phase suspension dispersion system, and stir 5min;
4), under the condition that is 550rpm at mixing speed, with water bath with thermostatic control, heat above-mentioned dispersion system, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 50 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, remove the external phase in anti-phase suspension dispersion system, with after deionized water rinsing, add 300mL to contain in 1.5% amylase solution except destarching, system is placed in to 200rpm shaking table at normal temperatures complete to starch degradation, with 5 washings of moisture of 10 times of volumes, and room temperature is flooded in 30% (v/v) acetum, then washs for 5 times with the moisture of 10 times of volumes, hygrometric state screening, obtains polyacrylamide reaming microballoon.Microballoon density is 1.21-1.41g/cm
3, size distribution is 110-209 μ m, and mean porosities is 88.2%, and pore size distribution is 0.7～1.2 μ m, and this microballoon can be used as a kind of novel expansion bed substrate.
Embodiment 7
1), by 3g acrylamide and 0.17g linking agent N, N '-methylene-bisacrylamide joins and in 15mL deionized water, is hybridly prepared into total mass concentration is 21% solution;
2) 1g tapioca (flour) is joined in 20mL deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous; 5g gelatinization of starch solution and 2g weighting agent metallic nickel particle, join in acrylamide/linking agent mixing solutions, mix and stir, under 20 ℃ of conditions, carry out ultrasonic dispersion, weighting agent uniform particles is dispersed in solution;
3) under 5 ℃ of conditions, using 0.135g initiator ammonium persulfate join in scattered solution and stirring and dissolving as disperse phase, disperse phase joins in the 20g hexanaphthene and 40g edible oil external phase that is dissolved with 1.8g sorbester p17, under the condition that is 350rpm at mechanical stirring rotating speed, form anti-phase suspension dispersion system, and stir 3min;
4), under the condition that is 350rpm at mixing speed, with water bath with thermostatic control, heat above-mentioned dispersion system, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 50 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, remove the external phase in anti-phase suspension dispersion system, with after deionized water rinsing, add 100mL to contain in 1% amylase solution except destarching, system is placed in to 150rpm shaking table at normal temperatures complete to starch degradation, with 4 washings of moisture of 5 times of volumes, and room temperature is flooded in 20% (v/v) acetum, then washs for 4 times with the moisture of 5 times of volumes, hygrometric state screening, obtains polyacrylamide reaming microballoon.Microballoon density is 1.11-1.22g/cm
3, size distribution is 105-295 μ m, and mean porosities is 80.7%, and pore size distribution is 0.6～1.1 μ m, and this microballoon can be used as a kind of novel expansion bed substrate.
Embodiment 8
1), by 7.1g acrylamide and 0.5g linking agent N, N '-methylene-bisacrylamide joins and in 15mL deionized water, is hybridly prepared into total mass concentration is 50% solution;
2) 1g tapioca (flour) is joined in 10mL deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous; 5g gelatinization of starch solution and 8g titanium dioxide nanoparticle, join in acrylamide/linking agent mixing solutions, mix and stir, under 25 ℃ of conditions, carry out ultrasonic dispersion, weighting agent uniform particles is dispersed in solution;
3) under 0 ℃ of condition, using 0.15g initiator ammonium persulfate join in scattered solution and stirring and dissolving as disperse phase, disperse phase joins in the 20g hexanaphthene and 40g edible oil external phase that is dissolved with 1.8g sorbester p17, under the condition that is 450rpm at mechanical stirring rotating speed, form anti-phase suspension dispersion system, and stir 5min;
4), under the condition that is 450rpm at mixing speed, with water bath with thermostatic control, heat above-mentioned dispersion system, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 50 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, remove the external phase in anti-phase suspension dispersion system, with after deionized water rinsing, add 100mL to contain in 1% amylase solution except destarching, system is placed in to 180rpm shaking table at normal temperatures complete to starch degradation, with 5 washings of moisture of 8 times of volumes, and room temperature is flooded in 25% (v/v) acetum, then washs for 5 times with the moisture of 8 times of volumes, hygrometric state screening, obtains polyacrylamide reaming microballoon.Microballoon density is 1.08-1.17g/cm
3, size distribution is 110-300 μ m, and mean porosities is 79.8%, and pore size distribution is 0.5～1.1 μ m, and this microballoon can be used as a kind of novel expansion bed substrate.
Claims (3)
1. a preparation method for Matrices for Expanded Bed Adsorption, is characterized in that comprising the steps:
1) monomer acrylamide and linking agent being mixed with to total mass concentration by the mixed in molar ratio of 40:1 ~ 30:1 is 20% ~ 50% solution;
2) starch is joined in deionized water, heated and stirred, to pasty state, is mixed with the Colloidal fluid of transparent homogeneous, i.e. gelatinization of starch solution, and the mass concentration of gelatinization of starch solution is 5% ~ 10%; Gelatinization of starch solution is joined in acrylamide/cross-linking agent solution that step 1) prepares, and the mass ratio that makes gelatinization of starch solution and acrylamide/cross-linking agent solution is 1:10 ~ 5:10; Add weighting agent particle, the mass ratio 0.1 ~ 1.3:1 of weighting agent particle and acrylamide/cross-linking agent solution, mixes and stirs, and under 20 ~ 35 ℃ of conditions, carries out ultrasonic dispersion, and weighting agent uniform particles is dispersed in solution;
3) under 0 ~ 5 ℃ of condition, initiator being joined to step 2) in the solution that obtains, the mass ratio of initiator and acrylamide is 2:100 ~ 5:100, stirs and becomes the disperse phase of preparation matrix; Disperse phase joins in the external phase that is dissolved with dispersion agent, and disperse phase and external phase mass ratio are 1:2 ~ 1:5, and dispersion agent is sorbester p17, and the mass percent in external phase is 2.5% ~ 4%; At mechanical stirring rotating speed, be under 350 ~ 550rpm, stir 3 ~ 5min, form anti-phase suspension dispersion system;
4), under the condition that is 350 ~ 550rpm at mixing speed, above-mentioned anti-phase suspension dispersion system is heated in water bath with thermostatic control, at N
2under protection, carry out inverse suspension polymerization reaction, temperature of reaction is 30 ~ 60 ℃, reacts 5 hours;
5) after having reacted, system is cooled to room temperature, removes the external phase in anti-phase suspension dispersion system, with deionized water rinsing, then add 1 ~ 2 times of volume
-amylase solution,
the massfraction of-amylase solution is 0.5% ~ 1.5%, system is at room temperature placed in to 100rpm ~ 300rpm shaking table complete to starch degradation, 4 ~ 5 washings of moisture with 5 ~ 10 times of volumes, and at 20% ~ 30%(v/v) room temperature dipping in acetum, use again 4 ~ 5 washings of moisture of 5 ~ 10 times of volumes, hygrometric state sieves, and obtains the polyacrylamide microsphere of macropore, and this microballoon is Matrices for Expanded Bed Adsorption.
2. the preparation method of a kind of novel Matrices for Expanded Bed Adsorption according to claim 1, is characterized in that described water soluble starch is commercially available wheat starch, tapioca (flour) or sweet potato starch; Weighting agent is titanium dioxide granule, stainless steel particle, nickel powder or tungsten carbide particle; Linking agent is N, N '-methylene-bisacrylamide; Initiator is ammonium persulphate; Dispersion agent is sorbester p17; External phase is the mixture of hexanaphthene and edible oil, and the mass ratio of hexanaphthene and edible oil is 1:1 ~ 1:5.
3. the Matrices for Expanded Bed Adsorption that as claimed in claim 1 prepared by preparation method, it is characterized in that Matrices for Expanded Bed Adsorption polymer network skeleton is polyacrylamide, weighting agent is embedded in polymer network skeleton, the size distribution of Matrices for Expanded Bed Adsorption is 100 ~ 300 μ m, and density is 1.02 ~ 1.40g/cm
3, mean porosities is 75% ~ 92%, aperture is 0.5 ~ 1.2 μ m.
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| CN106009030A (en) * | 2016-06-26 | 2016-10-12 | 周荣 | Preparation method of large-sized polyacrylamide cryogel |
| CN111334318A (en) * | 2020-03-18 | 2020-06-26 | 重庆三峡学院 | Method for preparing plant-based biochar from single component through biological activation and modification |
| CN113694248A (en) * | 2021-09-13 | 2021-11-26 | 中山大学 | Embolism microsphere based on soluble starch and preparation and application thereof |
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| 缪志俊等: "纤维素/不锈钢粉复合扩张床基质的制备", 《浙江大学学报(工学版)》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106009030A (en) * | 2016-06-26 | 2016-10-12 | 周荣 | Preparation method of large-sized polyacrylamide cryogel |
| CN106009030B (en) * | 2016-06-26 | 2019-05-07 | 周荣 | A kind of preparation method of large scale polyacrylamide crystalline substance glue |
| CN111334318A (en) * | 2020-03-18 | 2020-06-26 | 重庆三峡学院 | Method for preparing plant-based biochar from single component through biological activation and modification |
| CN111334318B (en) * | 2020-03-18 | 2021-07-27 | 重庆三峡学院 | Method for preparing plant-based biochar from single component through biological activation and modification |
| CN113694248A (en) * | 2021-09-13 | 2021-11-26 | 中山大学 | Embolism microsphere based on soluble starch and preparation and application thereof |
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