CN103145926A - Preparation method of wood element base polyacrylic acid microgel multiple-effect absorbing agent - Google Patents
Preparation method of wood element base polyacrylic acid microgel multiple-effect absorbing agent Download PDFInfo
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- CN103145926A CN103145926A CN2013100176517A CN201310017651A CN103145926A CN 103145926 A CN103145926 A CN 103145926A CN 2013100176517 A CN2013100176517 A CN 2013100176517A CN 201310017651 A CN201310017651 A CN 201310017651A CN 103145926 A CN103145926 A CN 103145926A
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- lignin
- polyacrylic acid
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- absorbing agent
- sorbent material
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- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 39
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002023 wood Substances 0.000 title claims abstract description 13
- 239000006096 absorbing agent Substances 0.000 title abstract 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002594 sorbent Substances 0.000 claims description 35
- 229920005610 lignin Polymers 0.000 claims description 29
- 239000002585 base Substances 0.000 claims description 25
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 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 6
- 239000003999 initiator Substances 0.000 claims description 6
- 241000228197 Aspergillus flavus Species 0.000 claims description 5
- 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
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 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
- 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
- 239000011837 N,N-methylenebisacrylamide 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
- 239000012535 impurity Substances 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 238000012216 screening 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
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 2
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 108090000526 Papain Proteins 0.000 abstract 1
- 239000004365 Protease Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 229940055729 papain Drugs 0.000 abstract 1
- 235000019834 papain Nutrition 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000003805 vibration mixing Methods 0.000 description 8
- 238000011068 loading method 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
- 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
- 238000011161 development Methods 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
- 239000003463 adsorbent Substances 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
- 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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- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 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
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- 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 groups 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
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing 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
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 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 invention relates to a preparation method of a wood element base polyacrylic acid microgel multiple-effect absorbing agent. The absorbing agent is prepared from the wood element of different sources. A moderate cross-linking agent is added in liquor containing the wood element according to the quality ratio which is 1:1-1:5 of the cross-linking agent and the wood element. A method of convention oil bath heating polymerization is adopted in temperature from 55 DEG C to 100 DEG C. The wood element base polyacrylic acid microgel multiple-effect absorbing agent reacts for 1 to 2 hours. Acrylic acid is added according to the quality ratio of 1:1-1:5 of the acrylic acid and the wood element. Moderate initiating agents are added. An accelerant is added at last. The wood element base polyacrylic acid microgel multiple-effect absorbing agent reacts for 1 to 2 hours under the temperature of 55 DEG C to 100 DEG C. The preparation method of the wood element base polyacrylic acid microgel multiple-effect absorbing agent has the advantages of being simple in preparation technology. The adsorption rate of the obtained absorbing agent is quick. Combining ability of the obtained absorbing agent is strong. The obtained absorbing agent is not easy to drop. Materials of heavy metal ion, zymoprotein and the like can be adsorbed at the same time. Adsorption capacity to Cu2+ can reach 76.7mg/g. Adsoprtion capacity of papain can reach 500.0mg/g. The adsorption process has no toxic side effects. Sources of the prepared raw materials are wide and convenient. Preparation cost is low.
Description
Technical field
The present invention relates to a kind of polymeric sorbent, is exactly a kind of preparation method of lignin-base polyacrylic acid microgel multiple-effect sorbent material, by this sorbent material can be comparatively fast the material such as Adsorption of Heavy Metal Ions, zymoprotein more.
Background technology
Xylogen as second largest natural biomass macromolecular material of reserves, is effectively to solve one of important channel of current fossil resource quagmire to its Efficient Development utilization.The annual plant-growth in the whole world can produce 1,500 hundred million tons of xylogen, and in papermaking wastewater, industrial lignin has 3,000 ten thousand tons.Xylogen is as the by product of wood saccharification industry and paper industry, mostly just utilized at present the Mierocrystalline cellulose more than 40% in the plant material, abandon with pollutent and remaining is rich in the precious resources such as xylogen, 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, caused the common concern of association area researchist and enterprise.
The adsorptive separation function material has very important purposes in a lot of fields, mainly comprises the aspect such as separation and purification, medical use, environment protection, solid phase organic synthesis, analytical technology of water treatment, separating organic matters purifying, hydrometallurgy, chemical industry preparation and purifying products, biologics.China's sorbent material that begins one's study the sixties in 20th century, using at present more, sorbent material mainly contains molecular sieve, gac and various ion exchange resin, polymeric adsorbent etc.In recent ten years, Chinese scholars replaces the more expensive gac of price or ion exchange resin etc. at the sorbent material of exploring Cheap highly effective.
The xylogen that separates from papermaking wastewater, cost specific activity charcoal is low.Owing to containing the oxy radicals such as numerous methoxyl groups, hydroxyl and carbonyl, for heavy metal ion or zymoprotein provide a large amount of adsorption sites, become the very good natural adsorbent of a class in lignin molecule.But because its oxy radical is numerous, especially easily causes and self assemble agglomeratingly, cause balling-up, pore-forming poor performance, cause the sorbent material loading capacity for preparing limited.Biological degradation can reduce its molecular weight, expose more adsorption site, if and can provide a supporter as " trunk ", and allow lignin molecule become " arm " and " hand ", just can give full play to the abilities such as hydrogen bond formation, chelating, complexing of numerous oxy radicals in lignin molecule and carry out material absorption, avoid simultaneously xylogen self because the factors such as hydrogen bond association are assembled agglomerating its adsorption effect that affects.Thereby can obtain to have multi-functional, high performance Lignin-Based Adsorption Material by the xylogen derivative reaction.Rarely have report about the Lignin-Based Adsorption Material development to the tool adsorptive separation function both at home and abroad so far, demand development urgently.
Summary of the invention
The present invention aims to provide a kind of preparation method of lignin-base polyacrylic acid microgel multiple-effect sorbent material, and simple, the prepared sorbent material of the method preparation technology can have larger adsorptive power to heavy metal ion, zymoprotein etc. simultaneously, and is with low cost.
Technical solution problem of the present invention adopts following technical scheme to be realized,
A kind of method of lignin-base polyacrylic acid microgel multiple-effect sorbent material is characterized in that, comprises following process:
1) utilize the black liquor of pulp making that contains alkali lignin after filtering and impurity removing, or the xylogen after purifying is dissolved in massfraction is in 0.5% ~ 3.0% sodium hydroxide solution.Be that 1:1 ~ 1:5 adds appropriate linking agent by linking agent and xylogen mass ratio in this solution, at 55 ~ 100 ℃ of lower oil bath heated polymerizables, reaction 1 ~ 2h;
2) in above-mentioned reaction solution, add vinylformic acid by vinylformic acid and xylogen mass ratio 1:1 ~ 1:5, add the initiator with the quality such as vinylformic acid, add at last the promotor with the quality such as vinylformic acid, 55 ~ 100 ℃ of reaction 1 ~ 2h.Reaction finishes by filtration, washing, drying, grinds, and prepares lignin-base polyacrylic acid microgel multiple-effect sorbent material.
The preparation method of described lignin-base polyacrylic acid microgel multiple-effect sorbent material is characterized in that: described xylogen is alkali lignin, sulfonated lignin, alkali lignin and sulfonated lignin after biological treatment.
The preparation method of described lignin-base polyacrylic acid microgel multiple-effect sorbent material is characterized in that: described alkali lignin be selected from agricultural crop straw, fiber-like the raw materials such as soil ulmin, wood materials and tankage thereof, fruit or its residue routinely alkaline pulping method preparation get.
The preparation method of described lignin-base polyacrylic acid microgel multiple-effect sorbent material is characterized in that:
Described alkali lignin and sulfonated lignin after biological treatment, be the aspergillus flavus strain F-1 (Aspergillus flavus strain F-1) that the screening gained has stronger lignin degradation ability from soil, it is in the lignin degradation substratum, and the liquid above fermented liquid of 5d of cultivating is through Sterile Filtration, drying, grinding gained.
The preparation method of described lignin-base polyacrylic acid microgel multiple-effect sorbent material is characterized in that: described linking agent is selected from a kind of in isocyanic ester, N,N methylene bis acrylamide, epoxy chloropropane.
The preparation method of described lignin-base polyacrylic acid microgel multiple-effect sorbent material is characterized in that: described initiator is selected from a kind of in ammonium persulphate, Potassium Persulphate, Sodium Persulfate.
The preparation method of described lignin-base polyacrylic acid microgel multiple-effect sorbent material is characterized in that: described promotor is selected from a kind of 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 sorbent material adsorption rate very fast (with respect to xylogen and polyacrylic acid), binding ability are strong, difficult drop-off;
2, sorbent material of the present invention can have larger adsorptive power (with respect to xylogen and polyacrylic acid) to heavy metal ion, zymoprotein simultaneously, for example, and during absorption 4h, to Cu
2+Loading capacity be 76.7mg/g, be 500.0mg/g to the loading capacity of papoid.
Description of drawings
The present invention is further illustrated below in conjunction with drawings and Examples.
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 lignin-base polyacrylic acid microgel multiple-effect sorbent material.
Embodiment
Below with specific embodiment, technical scheme of the present invention is described, but protection scope of the present invention is not limited to this:
The preparation and purification method of the described sorbent material raw material of embodiment 1:
1, the preparation and purification of alkali lignin
Take the rice straw after appropriate smashing, be that to add massfraction be 0.5% ~ 2.0% NaOH solution to 1:15 ~ 1:20 by stalk and NaOH solution quality volume ratio, adopt " method of disposing straws by sulfur trioxide gas " patented technology (patent No.: 200910116615), pass into SO
3Carry out pre-treatment effectively to peel off the xylogen on stalk top layer.Stirring reaction 7h in 55 ℃ of lower thermostat water baths, reaction solution repeatedly filter through two-layer gauze and namely get stalk black liquor (containing alkali lignin).Measure appropriate stalk black liquor, HCl solution to the pH value that drips wherein 2mol/L is 2 ~ 3, is placed in 55 ℃ of thermostat water baths and is incubated, until separate out a large amount of precipitations.Then reaction solution is processed 15min in the whizzer of 10000r/min, after the precipitation oven dry, grinding is sieved and is namely got the sour dead-wood quality of purifying.
2, the alkali lignin after biological treatment and the preparation of sulfonated lignin
In aspergillus flavus strain F-1 (Aspergillus flavus strain F-1) access 100mL lignin degradation substratum after the activation of LB substratum.The formula of lignin degradation substratum (g/L) wherein: 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 ℃ of sterilization 20min.Then be 7.0 at initial pH, in 30 ℃, cultivate in the shaking table incubator under the 150r/min condition, after 5d, time sampling filters, filtrate is after 80 ℃ of reduction vaporizations, and oven dry is ground to sieve and namely got alkali lignin (molecular weight≤1000) and sulfonated lignin (molecular weight≤528.61) after biological treatment.
Embodiment 2
Measure 150mL by the stalk black liquor (containing alkali lignin 0.28g, pH 〉=11) that the described method of embodiment 1 obtains, regulate pH to 9 with rare HCl, add 0.28g N, the N-methylene-bisacrylamide, stirring is fully dissolved it, pipettes simultaneously 0.7mL vinylformic acid in the 500mL round-bottomed flask, and add the 0.28g Potassium Persulphate, then the vibration dissolving adds the stalk black liquor, the vibration mixing, pipette wherein the 0.36mL Tetramethyl Ethylene Diamine, the vibration mixing.Be placed in oil bath pan and control 55 ℃ of temperature, react 4h under the inflated with nitrogen protection.Then filter, washing is to neutral, and 40 ℃ of vacuum-dryings obtain finished product and are put in the valve bag preservation after grinding.
The infared spectrum of xylogen, polyacrylic acid and xylogen/polyacrylic acid blend composition and the lignin-base polyacrylic acid microgel multiple-effect sorbent material chosen as shown in Figure 1.As seen from Figure 1, the characteristic group in the lignin molecule structure has clear and definite characteristic peak on infrared spectra, is mainly at 2930cm
-1There are the absorption of methyl, methylene radical and methyne, 1610-1600cm in the place
-1And 1520-1500cm
-1The place belongs to the aromatic nucleus skeletal vibration, at 1470-1460cm
-1There are the C-H flexural vibration of methyl and methylene radical at the place, at 1217cm
-1Typical syringaldehyde aromatic ring C-H stretching vibration is arranged, at 1515cm
-1And 1600cm
-1The place 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 the place, belongs to respectively asymmetric stretch bands of a spectrum and the symmetrical flexible bands of a spectrum of C=O.
In the infared spectrum of xylogen/polyacrylic acid blend composition, mainly contain two very strong absorption peaks, they are respectively 1575cm
-1The place belongs to asymmetric stretch bands of a spectrum and the 1423cm of C=O
-1The place belongs to the flexible bands of a spectrum of symmetry of C=O, substantially keeps polyacrylic characteristics of functional groups, and xylogen does not have obvious charateristic avsorption band to show therein, illustrates to fail physical blending preferably.
And in the infrared spectra of lignin-base polyacrylic acid microgel multiple-effect sorbent material, have 1600cm
-1The charateristic avsorption band of place's xylogen belongs to the 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 is compared with xylogen all and is changed to some extent.This explanation is under the effect of initiator, linking agent and promotor, and the intermolecular existence of lignin molecule and polyacrylic acid interacts, rather than only limits to physical blending effect preferably.And transmission electron microscope observing is found (as shown in Figure 2), and synthetic product all can form nano level microballoon shape in solvent, and size distribution is in 600nm-1.2 μ m left and right.And spherical more, have very large surface-area, better dispersed, fully contact so be easy to the adsorbates such as heavy metal ion or protein molecule, be comparatively ideal sorbent material form.
Embodiment 3
Take the alkali lignin 1.12g more than biological treatment 5d, add in 150mL2%NaOH (massfraction) solution, regulate pH to 9 with rare HCl.Add 0.28g N, the N-methylene-bisacrylamide, stirring is fully dissolved it, pipette simultaneously 0.7mL vinylformic acid in the 500mL round-bottomed flask, and add the 0.28g Potassium Persulphate, the vibration dissolving, then black liquor is added in the vinylformic acid system, the vibration mixing pipettes the 0.36mL Tetramethyl Ethylene Diamine wherein, the vibration mixing.Be placed in oil bath pan and control 100 ℃ of temperature, react 4h under nitrogen protection.Then filter, washing is to neutral, and 40 ℃ of vacuum-dryings obtain finished product and are put in the valve bag preservation after grinding.
Take respectively 0.15g lignin-base polyacrylic acid microgel multiple-effect sorbent material product, and add in the 100mL Erlenmeyer flask, then add the newly Cu of the 2g/L of configuration of 100mL in each Erlenmeyer flask
2+(be designated as c
0) solution, the vibration mixing is placed in 50 ℃ of constant-temperature tables and adsorbs 4h, and then suction filtration to remove precipitation, obtains filtrate and uses iodometric titrationiodimetry titration Cu
2+Content (being 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 the rear solution of absorption
2+Concentration;
W is the over dry quality that takes sorbent material.
The result demonstration, (xylogen: vinylformic acid) be 4:1, pH value of reaction system is 9, and when temperature of reaction was 100 ℃, the lignin-base carbopol gel product of preparation gained was to Cu at feed ratio
2+Have the optimal adsorption performance, it is to Cu
2+Loading capacity can reach 76.7mg/g.
Embodiment 4
Take the alkali lignin 0.28g more than biological treatment 5d, add in 150mL2%NaOH (massfraction) solution, regulate pH to 9 with rare HCl.Add 0.28g linking agent N, the N-methylene-bisacrylamide, stirring is fully dissolved it, pipette simultaneously 0.7mL vinylformic acid in the 500mL round-bottomed flask, and add the 0.28g initiator potassium persulfate, the vibration dissolving, then black liquor is added in the vinylformic acid system, the vibration mixing pipettes 0.36mL promotor Tetramethyl Ethylene Diamine wherein, the vibration mixing.Be placed in oil bath pan and control 100 ℃ of temperature, react 4h under nitrogen protection.Then filter, washing is to neutral, and 40 ℃ of vacuum-dryings obtain finished product and are put in the valve bag preservation after grinding.
Accurately taking quality w is that the 10mg papoid is dissolved in the PBS buffered soln of 10mLpH=7, separately accurately takes respectively quality w
1For 10mg lignin-base carbopol gel product also adds respectively in papoid PBS solution, the vibration mixing is placed in 30 ℃ of constant-temperature tables and adsorbs 4h.Then pipette 1mL solution centrifugal 10min of 10000r/min in the 10mL centrifuge tube with transfer pipet.Double separation of supernatant and precipitation, each precipitation adds the dissolving of 1mL distilled water, more centrifugal 10min.The supernatant liquor merging is settled to 10mL, adds 5mL water dilution dissolving in precipitation.
The detection of papoid content: supernatant liquor and former precipitation diluent after getting respectively 1mL and processing add the Coomassie brilliant blue G250 protein reagent of the new preparation of 5mL, in 595nm place its light absorption value of mensuration.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, and X is the OD value, R
2=0.999.
The calculating of gel absorption papoid capacity: the ratio a in the protein content sum is as the absorption Estimation of proportion of gel in precipitation and supernatant liquor with contained protein content in precipitation, and loading capacity q (mg/g) calculates by formula (b).
Result shows, is 1:1 at feed ratio, and pH value of reaction system is 9, and when temperature of reaction was 100 ℃, the xylogen of preparation gained-carbopol gel product had the optimal adsorption performance to papoid, and its loading capacity to papoid can reach 500.0mg/g.
Claims (7)
1. the preparation method of a lignin-base polyacrylic acid microgel multiple-effect sorbent material is characterized in that: comprise following process:
1) utilize the black liquor of pulp making that contains alkali lignin after filtering and impurity removing, or the xylogen after purifying is dissolved in massfraction is in 0.5% ~ 3.0% sodium hydroxide solution, be that 1:1 ~ 1:5 adds appropriate linking agent by linking agent and xylogen mass ratio in this solution, at 55 ~ 100 ℃ of lower oil bath heated polymerizables, reaction 1 ~ 2h;
2) in above-mentioned reaction solution, add vinylformic acid by vinylformic acid and xylogen mass ratio 1:1 ~ 1:5, the initiator of the quality such as interpolation and vinylformic acid, add at last the promotor with quality such as vinylformic acid, 55 ~ 100 ℃ of reaction 1 ~ 2h, reaction finishes by filtration, washing, drying, grinds, and prepares lignin-base polyacrylic acid microgel multiple-effect sorbent material.
2. the preparation method of lignin-base polyacrylic acid microgel multiple-effect sorbent material according to claim 1 is characterized in that:
Described xylogen is alkali lignin, sulfonated lignin, alkali lignin and sulfonated lignin after biological treatment.
3. the preparation method of lignin-base polyacrylic acid microgel multiple-effect sorbent material according to claim 1 is characterized in that:
Described alkali lignin be selected from agricultural crop straw, fiber-like the raw materials such as soil ulmin, wood materials and tankage thereof, fruit or its residue routinely alkaline pulping method preparation get.
4. the preparation method of lignin-base polyacrylic acid microgel multiple-effect sorbent material according to claim 1 is characterized in that:
Described alkali lignin and sulfonated lignin after biological treatment, be the aspergillus flavus strain F-1 that the screening gained has stronger lignin degradation ability from soil, it is in the lignin degradation substratum, and the liquid above fermented liquid of 5d of cultivating is through Sterile Filtration, drying, grinding gained.
5. the preparation method of lignin-base polyacrylic acid microgel multiple-effect sorbent material according to claim 1 is characterized in that:
Described linking agent is selected from a kind of in isocyanic ester, N,N methylene bis acrylamide, epoxy chloropropane.
6. the preparation method of lignin-base polyacrylic acid microgel multiple-effect sorbent material according to claim 1 is characterized in that:
Described initiator is selected from a kind of in ammonium persulphate, Potassium Persulphate, Sodium Persulfate.
7. the preparation method of lignin-base polyacrylic acid microgel multiple-effect sorbent material according to claim 1 is characterized in that: described promotor is selected from a kind of in triethylene diamine, Tetramethyl Ethylene Diamine, dibutyl tin laurate.
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