CN103145926B - The preparation method of a kind of base polyacrylic acid microgel multi-effect adsorption agent - Google Patents
The preparation method of a kind of base polyacrylic acid microgel multi-effect adsorption agent Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 31
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 29
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920005610 lignin Polymers 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000002585 base Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 18
- 229920001732 Lignosulfonate Polymers 0.000 claims description 9
- 235000019357 lignosulphonate Nutrition 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 241000228197 Aspergillus flavus Species 0.000 claims description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000000855 fermentation Methods 0.000 claims description 2
- 230000004151 fermentation Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000011146 sterile filtration Methods 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 abstract description 10
- 238000011068 loading method Methods 0.000 abstract description 8
- 239000003463 adsorbent Substances 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 231100000957 no side effect Toxicity 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 8
- 238000003805 vibration mixing Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000274 adsorptive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- YVNQAIFQFWTPLQ-UHFFFAOYSA-O [4-[[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfophenyl)methyl]amino]-2-methylphenyl]methylidene]-3-methylcyclohexa-2,5-dien-1-ylidene]-ethyl-[(3-sulfophenyl)methyl]azanium Chemical compound C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S(O)(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S(O)(=O)=O)C)C=C1 YVNQAIFQFWTPLQ-UHFFFAOYSA-O 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- -1 methoxyl group Chemical group 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
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- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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Abstract
The present invention relates to the preparation method of a kind of base polyacrylic acid microgel multi-effect adsorption agent.This sorbent material with the xylogen of different sources for raw material, be add appropriate linking agent at 1: 1 ~ 1: 5 by linking agent and lignin quality ratio in containing the solution of xylogen, the method of conventional oil bath heated polymerizable is adopted at 55 ~ 100 DEG C, reaction 1 ~ 2h, vinylformic acid is added than 1: 1 ~ 1: 5 again by vinylformic acid and lignin quality, add appropriate initiator, finally add promotor, 55-100 DEG C of reaction 1 ~ 2h.The invention has the advantages that: preparation technology is simple, obtained adsorbent speed is fast, binding ability strong, difficult drop-off; And the energy material such as Adsorption of Heavy Metal Ions, zymoprotein simultaneously, to Cu
2+loading capacity can reach 76.7mg/g, can 500.0mg/g be reached to the loading capacity of papoid; And adsorption process has no side effect, raw materials wide material sources are convenient, and preparation cost is cheaper.
Description
Technical field
The present invention relates to a kind of polymeric sorbent, is exactly the preparation method of a kind of base polyacrylic acid microgel multi-effect adsorption agent, can the very fast more material such as Adsorption of Heavy Metal Ions, zymoprotein by this sorbent material.
Background technology
Xylogen is as the second largest natural biomass macromolecular material of reserves, and utilizing its Efficient Development is effective one of important channel solving current fossil resource quagmire.The annual plant-growth in the whole world can produce 1,500 hundred million tons of xylogen, and in papermaking wastewater, industrial wood have 3,000 ten thousand tons.Xylogen is as wood saccharification industry and the by product of paper industry, mostly just make use of the Mierocrystalline cellulose more than 40% in plant material at present, and remaining is rich in the precious resources such as xylogen and abandons with pollutent, cause the significant wastage of resource and the severe contamination of environment.Therefore, how to effectively utilize this renewable resources of xylogen, improve its added value, cause the common concern of association area researchist and enterprise.
Adsorptive separation function material has very important purposes in a lot of fields, mainly comprise water treatment, separating organic matters purifying, hydrometallurgy, chemical industry preparation with purifying products, biologics the aspect such as separation and purification, medical use, environment protection, Solid-phase organic synthesis, analytical technology.China begins one's study the sixties in 20th century sorbent material, applies more sorbent material at present and mainly contains molecular sieve, gac and various ion exchange resin, polymeric adsorbent etc.In recent ten years, Chinese scholars is exploring the sorbent material of Cheap highly effective, replaces price gac costly or ion exchange resin etc.
The xylogen be separated from papermaking wastewater, cost specific activity charcoal is low.Due to containing oxy radicals such as numerous methoxyl group, hydroxyl and carbonyls in lignin molecule, for heavy metal ion or zymoprotein provide a large amount of adsorption sites, become the natural adsorbent that a class is very excellent.But because its oxy radical is numerous, especially easily cause self assemble agglomerating, cause balling-up, pore-forming poor performance, cause the adsorbent finite capacity prepared.Biological degradation can reduce its molecular weight, expose more adsorption site, and if a supporter can be provided as " trunk ", and allow lignin molecule become " arm " and " hand ", the ability such as hydrogen bond formation, chelating, complexing that just can give full play to numerous oxy radical in lignin molecule carries out species adsorbs, and that avoids xylogen self agglomeratingly affects its adsorption effect because the factors such as hydrogen bond association are assembled simultaneously.Thus can be obtained by xylogen derivative reaction and there is multi-functional, high performance Lignin-Based Adsorption Material.Domestic and international so far rarely have report about to the Lignin-Based Adsorption Material development of tool adsorptive separation function, urgently develops.
Summary of the invention
The present invention aims to provide the preparation method of a kind of base polyacrylic acid microgel multi-effect adsorption agent, and simple, the prepared sorbent material of the method preparation technology heavy metal ion, zymoprotein etc. can have larger adsorptive power simultaneously, with low cost.
Technical solution problem of the present invention adopts following technical scheme to be realized,
A method for base polyacrylic acid microgel multi-effect adsorption agent, is characterized in that, comprises following process:
1) utilize after filtering and impurity removing containing the black liquor of pulp making of alkali lignin, or the xylogen after purifying to be dissolved in massfraction be in the sodium hydroxide solution of 0.5% ~ 3.0%.Appropriate linking agent is added by linking agent and lignin quality than for 1:1 ~ 1:5, oil bath heated polymerizable at 55 ~ 100 DEG C, reaction 1 ~ 2h in this solution;
2) in above-mentioned reaction solution, add vinylformic acid by vinylformic acid and lignin quality than 1:1 ~ 1:5, add the initiator with the quality such as vinylformic acid, finally add the promotor with the quality such as vinylformic acid, 55 ~ 100 DEG C of reaction 1 ~ 2h.Through filtration, washing, dry, grinding after reaction terminates, prepare the agent of base polyacrylic acid microgel multi-effect adsorption.
The preparation method of described base polyacrylic acid microgel multi-effect adsorption agent, is characterized in that: described xylogen be alkali lignin, sulfonated lignin, through biological treatment after alkali lignin and sulfonated lignin.
The preparation method of described base polyacrylic acid microgel multi-effect adsorption agent, is characterized in that: described alkali lignin be selected from the raw materials such as agricultural crop straw, the soil ulmin of fiber-like, wood materials and tankage, fruit or its residue routinely alkaline pulping method preparation get.
The preparation method of described base polyacrylic acid microgel multi-effect adsorption agent, is characterized in that:
The described alkali lignin after biological treatment and sulfonated lignin, be and screen the aspergillus flavus strain F-1 (AspergillusflavusstrainF-1) that gained has stronger lignin degradation ability from soil, it is in lignin degradation substratum, the fermentation liquor Sterile Filtration of liquid cultivation more than 5d, drying, grinding gained.
The preparation method of described base polyacrylic acid microgel multi-effect adsorption agent, is characterized in that: described linking agent is selected from the one in isocyanic ester, N,N methylene bis acrylamide, epoxy chloropropane.
The preparation method of described base polyacrylic acid microgel multi-effect adsorption agent, is characterized in that: described initiator is selected from the one in ammonium persulphate, Potassium Persulphate, Sodium Persulfate.
The preparation method of described base polyacrylic acid microgel multi-effect adsorption agent, is characterized in that: described promotor is selected from the one in triethylene diamine, Tetramethyl Ethylene Diamine, dibutyl tin laurate.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, absorbent preparation technique of the present invention is simple, and obtained adsorbent speed very fast (relative to xylogen and polyacrylic acid), binding ability are strong, difficult drop-off;
2, sorbent material of the present invention heavy metal ion, zymoprotein can have larger adsorptive power (relative to xylogen and polyacrylic acid) simultaneously, such as, during absorption 4h, to Cu
2+loading capacity be 76.7mg/g, be 500.0mg/g to the loading capacity of papoid.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further illustrated.
Fig. 1 is the infrared spectrogram of xylogen, polyacrylic acid and xylogen/polyacrylic acid blend composition and synthesized gel rubber.
Fig. 2 is the transmission electron microscope picture of base polyacrylic acid microgel multi-effect adsorption agent.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
The preparation and purification method of adsorbent material described in embodiment 1:
1, the preparation and purification of alkali lignin
Take the rice straw after appropriate smashing, be the NaOH solution that 1:15 ~ 1:20 adds that massfraction is 0.5% ~ 2.0% by stalk and NaOH solution mass volume ratio, (patent No.: 200910116615), passes into SO to adopt " method of disposing straws by sulfur trioxide gas " patented technology
3carry out pre-treatment effectively to peel off the xylogen on stalk top layer.Stirring reaction 7h in thermostat water bath at 55 DEG C, reaction solution repeatedly filters through two-layer gauze and obtains stalk black liquor (containing alkali lignin).Measure appropriate stalk black liquor, the HCl solution dripping 2mol/L is wherein 2 ~ 3 to pH value, is placed in 55 DEG C of thermostat water baths and is incubated, until separate out a large amount of precipitation.Then reaction solution is processed 15min in the whizzer of 10000r/min, precipitation grinds the sour dead-wood quality sieving and obtain purifying after drying.
2, the alkali lignin after biological treatment and the preparation of sulfonated lignin
Aspergillus flavus strain F-1 (AspergillusflavusstrainF-1) after the activation of LB substratum accesses in 100mL lignin degradation substratum.The wherein formula (g/L) of lignin degradation substratum: alkali lignin or sodium lignosulfonate 2.0, glucose 0.5, (NH
4)
2sO
41.5, KH
2pO
41.5, K
2hPO
41.5, MgSO
47H
2o0.2, NaCl0.2, FeSO
40.05, MnSO
40.02, pH7.4, constant volume 1L, 121 DEG C of sterilizing 20min.Then be 7.0 at initial pH, in 30 DEG C, cultivate in shaking table incubator under 150r/min condition, after 5d, time sampling filters, filtrate, after 80 DEG C of reduction vaporizations, dries and grinds the alkali lignin (molecular weight≤1000) after sieving and obtain biological treatment and sulfonated lignin (molecular weight≤528.61).
Embodiment 2
Measure the stalk black liquor (containing alkali lignin 0.28g, pH >=11) that 150mL obtains by method described in embodiment 1, regulate pH to 9 with rare HCl, add 0.28gN, N-methylene-bisacrylamide, stirs and makes it fully dissolve, pipette 0.7mL vinylformic acid simultaneously in 500mL round-bottomed flask, and add 0.28g Potassium Persulphate, vibration is dissolved, and then adds stalk black liquor, vibration mixing, pipette 0.36mL Tetramethyl Ethylene Diamine wherein, vibration mixing.Be placed in oil bath pan control temperature 55 DEG C, under inflated with nitrogen protection, react 4h.Then filter, washing is to neutral, and 40 DEG C of vacuum-dryings, obtain finished product and be put in valve bag preservation after grinding.
Xylogen, polyacrylic acid and xylogen/polyacrylic acid blend composition and the infared spectrum of base polyacrylic acid microgel multi-effect adsorption agent chosen are as shown in Figure 1.As seen from Figure 1, the characteristic group in lignin molecule structure has clear and definite characteristic peak on infrared spectra, mainly at 2930cm
-1there is the absorption of methyl, methylene radical and methyne at place, 1610-1600cm
-1and 1520-1500cm
-1place belongs to aromatic nucleus skeletal vibration, at 1470-1460cm
-1there are the C-H flexural vibration of methyl and methylene radical at place, at 1217cm
-1there is typical syringaldehyde aromatic ring C-H stretching vibration, at 1515cm
-1and 1600cm
-1place is the vibration of aromatic nucleus.
Polyacrylic infared spectrum is fairly simple polymer spectrum, at 1623cm
-1, 1400cm
-1there are two stronger absorption peaks at place, belongs to the asymmetric stretch bands of a spectrum of C=O and symmetry respectively and to stretch bands of a spectrum.
In the infared spectrum of xylogen/polyacrylic acid blend composition, mainly contain two very strong absorption peaks, they are 1575cm respectively
-1place belongs to asymmetric stretch bands of a spectrum and the 1423cm of C=O
-1the symmetry that place belongs to C=O is stretched bands of a spectrum, substantially keeps polyacrylic characteristics of functional groups, and xylogen does not have obvious charateristic avsorption band to show wherein, illustrates to fail physical blending preferably.
And in the infrared spectra of base polyacrylic acid microgel multi-effect adsorption agent, there is 1600cm
-1the charateristic avsorption band of place's xylogen, belongs to aromatic nucleus skeletal vibration, and 1560cm
-1the absorption peak at place belongs to the asymmetric stretch bands of a spectrum of C=O key, is polyacrylic charateristic avsorption band.The absorption peak of other functional groups changes all to some extent compared with xylogen.This illustrates under the effect of initiator, linking agent and promotor, lignin molecule and polyacrylic acid intermolecular exist interact, instead of be only limitted to good physical blending effect.And transmission electron microscope observing finds (as shown in Figure 2), synthetic product all can form nano level microballoon shape in a solvent, and size distribution is at about 600nm-1.2 μm.And spherical more, have very large surface-area, better dispersed, fully contacting so be easy to the adsorbate such as heavy metal ion or protein molecule, is comparatively ideal sorbent material form.
Embodiment 3
Take the alkali lignin 1.12g through more than the 5d that carries out a biological disposal upon, add in 150mL2%NaOH (massfraction) solution, regulate pH to 9 with rare HCl.Add 0.28gN, N-methylene-bisacrylamide, stirring makes it fully dissolve, pipette 0.7mL vinylformic acid simultaneously in 500mL round-bottomed flask, and add 0.28g Potassium Persulphate, vibration is dissolved, then black liquor is added in acrylic system, vibration mixing, pipettes 0.36mL Tetramethyl Ethylene Diamine wherein, vibration mixing.Be placed in oil bath pan control temperature 100 DEG C, under nitrogen protection, react 4h.Then filter, washing is to neutral, and 40 DEG C of vacuum-dryings, obtain finished product and be put in valve bag preservation after grinding.
Take 0.15g base polyacrylic acid microgel multi-effect adsorption agent product respectively, and add in 100mL Erlenmeyer flask, in each Erlenmeyer flask, then add the Cu of the 2g/L that 100mL newly configures
2+(be designated as c
0) solution, vibration mixing is placed in 50 DEG C of constant-temperature tables adsorbs 4h, and then suction filtration is to remove precipitation, obtains filtrate and uses iodometric titrationiodimetry titration Cu
2+content (be designated as c), and calculate the loading capacity of prepared gel by formula (a).
Wherein, c
0for adsorbing Cu in front solution
2+concentration;
C is Cu in solution after absorption
2+concentration;
W is the absolute dry mass taking sorbent material.
Result shows, and be 4:1 at feed ratio (xylogen: vinylformic acid), pH value of reaction system is 9, when temperature of reaction is 100 DEG C, prepares the base polyacrylic acid gel product of gained to Cu
2+have optimal adsorption performance, it is to Cu
2+loading capacity can reach 76.7mg/g.
Embodiment 4
Take the alkali lignin 0.28g through more than the 5d that carries out a biological disposal upon, add in 150mL2%NaOH (massfraction) solution, regulate pH to 9 with rare HCl.Add 0.28g linking agent N, N-methylene-bisacrylamide, stirring makes it fully dissolve, pipette 0.7mL vinylformic acid simultaneously in 500mL round-bottomed flask, and add 0.28g initiator potassium persulfate, vibration is dissolved, then black liquor is added in acrylic system, vibration mixing, pipettes 0.36mL promotor Tetramethyl Ethylene Diamine wherein, vibration mixing.Be placed in oil bath pan control temperature 100 DEG C, under nitrogen protection, react 4h.Then filter, washing is to neutral, and 40 DEG C of vacuum-dryings, obtain finished product and be put in valve bag preservation after grinding.
Accurately taking quality w is that 10mg papoid is dissolved in the PBS buffered soln of 10mLpH=7, separately accurately takes quality w respectively
1for 10mg base polyacrylic acid gel product also adds in papoid PBS solution respectively, vibration mixing is placed in 30 DEG C of constant-temperature tables adsorbs 4h.Then 1mL solution centrifugal 10min of 10000r/min in 10mL centrifuge tube is pipetted with transfer pipet.Double separation of supernatant and precipitation, each precipitation adds 1mL distilled water and dissolves, more centrifugal 10min.Supernatant liquor merging is settled to 10mL, adds the dilution of 5mL water and dissolve in precipitation.
The detection of papoid content: get the supernatant liquor after 1mL process and former precipitation diluent respectively, add the Coomassie brilliant blue G250 protein reagent that 5mL newly prepares, measures its light absorption value in 595nm place.And calculate remaining enzyme content according to typical curve.Fit equation is Y=171.28X-7.5364, and wherein Y is protein content, and unit is μ g, X is OD value, R
2=0.999.
The calculating of gel adsorption papoid capacity: precipitating and the estimation of the ratio a in protein content sum in supernatant liquor as the adsorption ratio of gel with protein content contained in precipitation, loading capacity q (mg/g) calculates by formula (b).
Result shows, and be 1:1 at feed ratio, pH value of reaction system is 9, and when temperature of reaction is 100 DEG C, the xylogen-carbopol gel product preparing gained has optimal adsorption performance to papoid, and it can reach 500.0mg/g to the loading capacity of papoid.
Claims (1)
1. the preparation method of base polyacrylic acid microgel multi-effect adsorption agent, it is characterized in that: comprise following process: 1) utilize the black liquor of pulp making containing alkali lignin after filtering and impurity removing, or the xylogen after purifying is dissolved in massfraction is in the sodium hydroxide solution of 0.5% ~ 3.0%, appropriate linking agent is added by linking agent and lignin quality than for 1:1 ~ 1:5 in this solution, oil bath heated polymerizable at 55 ~ 100 DEG C, reaction 1 ~ 2h;
2) in above-mentioned reaction solution, vinylformic acid is added than 1:1 ~ 1:5 by vinylformic acid and lignin quality, the initiator of the quality such as interpolation and vinylformic acid, finally add the promotor with quality such as vinylformic acid, 55 ~ 100 DEG C of reaction 1 ~ 2h, through filtration, washing, dry, grinding after reaction terminates, prepare the agent of base polyacrylic acid microgel multi-effect adsorption;
Described xylogen be alkali lignin, sulfonated lignin, through biological treatment after alkali lignin and sulfonated lignin;
Described alkali lignin be selected from agricultural crop straw, the soil ulmin of fiber-like, wood materials and tankage, fruit or its residue routinely alkaline pulping method preparation get;
The described alkali lignin after biological treatment and sulfonated lignin, be and screen the aspergillus flavus strain F-1 that gained has stronger lignin degradation ability from soil, it is in lignin degradation substratum, the fermentation liquor Sterile Filtration of liquid cultivation more than 5d, drying, grinding gained;
Described linking agent is selected from the one in isocyanic ester, N,N methylene bis acrylamide, epoxy chloropropane;
Described initiator is selected from the one in ammonium persulphate, Potassium Persulphate, Sodium Persulfate;
Described promotor is selected from the one in triethylene diamine, Tetramethyl Ethylene Diamine, dibutyl tin laurate.
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