CN100537021C - Method for preparing ammonifiers adosorbant - Google Patents
Method for preparing ammonifiers adosorbant Download PDFInfo
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- CN100537021C CN100537021C CNB2007100649483A CN200710064948A CN100537021C CN 100537021 C CN100537021 C CN 100537021C CN B2007100649483 A CNB2007100649483 A CN B2007100649483A CN 200710064948 A CN200710064948 A CN 200710064948A CN 100537021 C CN100537021 C CN 100537021C
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- mycelium
- organic solvent
- adsorbent
- adosorbant
- ammonifiers
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- 238000000034 method Methods 0.000 title claims description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 8
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical group ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 6
- 241000228150 Penicillium chrysogenum Species 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- 241000233866 Fungi Species 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- CDIIZULDSLKBKV-UHFFFAOYSA-N 4-chlorobutanoyl chloride Chemical compound ClCCCC(Cl)=O CDIIZULDSLKBKV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- FBSMERQALIEGJT-UHFFFAOYSA-N chlorpromazine hydrochloride Chemical compound [H+].[Cl-].C1=C(Cl)C=C2N(CCCN(C)C)C3=CC=CC=C3SC2=C1 FBSMERQALIEGJT-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000333 poly(propyleneimine) Polymers 0.000 claims description 3
- 230000001954 sterilising effect Effects 0.000 claims description 3
- 238000004659 sterilization and disinfection Methods 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 abstract description 45
- 125000003277 amino group Chemical group 0.000 abstract 4
- 229920002521 macromolecule Polymers 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000004176 ammonification Methods 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 13
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- HCJLVWUMMKIQIM-UHFFFAOYSA-M sodium;2,3,4,5,6-pentachlorophenolate Chemical compound [Na+].[O-]C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl HCJLVWUMMKIQIM-UHFFFAOYSA-M 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001411320 Eriogonum inflatum Species 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
- 241000602909 Lyngbya taylorii Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000235527 Rhizopus Species 0.000 description 1
- 241000235546 Rhizopus stolonifer Species 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
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- 239000012138 yeast extract Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a preparation method of ammoniated mycelium adsorbent, in particular, it provides a preparation method of mycelium adsorbent whose surface has positive charge. Said invention can make macromolecular polymer containing lots of amino-group be grafted on the mycelium surface by means of two-step simple chemical reaction so as to greatly raise the density of adsorbent surface amino-groups. Its preparation method includes the following steps: using mycelium as raw material, firstly, adding mycelium into an organic solvent of cross-linking agent and making reaction for 8-24h, the volume weight ratio of cross-linking agent and mycelium is 0.5-4ml/g, then adding mycelium into an organic solvent containing amino-group macromolecule, the weight volume ratio of amino-group macromolecule and organic solvent is 5-20g/100ml, heating to 80-100deg.C and making reaction for 10-24h so as to obtain the invented ammoniated mycelium adsorbent.
Description
Technical field
The invention belongs to water treatment adsorption technology field.Be particularly related to and be used for adsorbing the preparation method who contains a kind of ammonifiers adosorbant of anion incretion interferent in the removal waste water.
Background technology
Mycelium is the byproduct of brewageing with pharmaceutical industry, and part is as animal feed, and major part is dropped, and not only wastes resource, also contaminated environment.In recent years, utilize mycelium to cause people's common concern as the adsorbent of heavy metal, but because the functional group densities on promycelium surface is low, its adsorbance often not high (usually less than 20mg/g).Therefore, improve the focus that mycelial adsorption capacity becomes research by surface modification.
Modal is to handle mycelium with NaOH, to improve its adsorption capacity.People such as Tan Tianwei have reported with 0.5M NaOH and had handled mycelium 3 hours that after the clean dry, this adsorbent is to Ni
2+Adsorbance reach about 20mg/g (BioseparationEngineering, 2000,169-173).People such as Tu Juan " nonactive rhizopus is to the absorption of heavy metal ions in wastewater " (environmental science, 1994,16 (1), reported that the mycelial adsorbance after 0.5M NaOH handles has improved 25% in 12-15).It is reported, phosphate, amino, functional group's graftings such as carboxyl improve mycelial adsorption capacity to material surface energy.People such as Klimmek (Environmental Science and Technology, 2001,35,4283-4288) reported marine alga (Lyngbyataylorii) after phosphorylation is handled, maximal absorptive capacity significantly improves.Bai and Abraham (Water Research, 2002,36,1224-1236) discover that fungi (Rhizopus nigricans) mycelium is introduced amino and carboxyl after, be used for the maximal absorptive capacity of adsorbing hexavalent chromium and reach 200mg/g.Studies show that (Water Research, 2003,37,4544-4552), with surfactant (bromination hexadecane base trimethylamine) and cationic polyelectrolyte modification paecilomycerol filament, can significantly improve the adsorption capacity of anion As (V), when pH=3, maximal absorptive capacity reaches 57.85mg/g.Tan Tianwei etc. (Enzyme andmicrobial Technology, 2004,35,508-513) reported and utilize the ammoniacal liquor can ammonification paecilomycerol filament, improve the amino density of mycelium surface, thereby improved mycelium heavy metal Ni
2+Adsorbance; They also utilize molecular imprinting that shitosan is coated on mycelium surface, be used for handling the sewage that contains heavy metal (pay CHIGO, Su Haijia, Tan Tianwei, the chemical industry journal, 2004,55,958-962).The mycelium adsorbent of report is mainly used to adsorb heavy metal at present, seldom is used for adsorbing the removal organic pollution.
Amino can not only and complexing of metal ion, and be easy to protonated, by anionic pollutant in the electrostatic interaction adsorbed water.Because the colloid in the water has negative electrical charge usually, the adsorbent that has positive charge is easy to the adsorpting anion pollutant.Amino grafting can be made the adsorbent of surperficial positively charged to material surface.
Many researchers has been carried out the number of chemical modification at mycelium, its objective is to improve its surperficial functional group densities, and then improves the adsorbance of mycelium adsorbent.Because mycelial specific area is less, absorption mainly occurs in mycelium surface, and therefore, it is limited that the functional group densities of traditional chemical reaction pair mycelium surface improves degree, causes the adsorbance increase not remarkable.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of ammonifiers adosorbant, by containing amino big molecule grafting under given conditions to mycelium surface, obtain the positively charged ammonifiers adosorbant in surface, thereby further improve the adsorption capacity of mycelium adsorbent.
Technical scheme of the present invention is as follows:
A kind of preparation method of ammonifiers adosorbant is characterized in that this method carries out as follows:
1) with the mycelium is raw material, mycelium sterilization back is cleaned with deionized water, be stored in the drier after the freeze drying;
2) dried mycelium is joined in chloroform or the dimethyl formamide organic solvent, the w/v of mycelium and organic solvent is 1～2.5g/100mL, dropwise add glue crosslinking agent then, glue crosslinking agent and mycelial envelope-bulk to weight ratio are 0.5～4mL/g, after the seal of vessel at 25～100 ℃ down behind reaction 8～24h, filter mycelium, and clean with chloroform or dimethyl formamide organic solvent;
3) with step 2) mycelium that obtains puts into and contains amino macromolecular chloroform or solvent dimethylformamide, the described w/v that contains amino big molecule and organic solvent is 5～20g/100mL, the w/v of mycelium and organic solvent is 0.5～2g/100mL, then at 80～100 ℃ of reaction 10～24h; Filtration obtains mycelium, uses earlier methyl alcohol, and the responseless reagent of mycelium surface is cleaned with deionized water in the back, obtains ammonifiers adosorbant, and freeze drying is to constant weight.
Used mycelium is Penicillium notatum or citric acid fungus mycelium among the present invention.Used glue crosslinking agent is chloracetyl chloride, chlorpromazine chloride, chlorobutanoylchloride or epoxychloropropane.The used big molecule that contains amino is polymine, polyethylene polyamine, diamine butane polypropylene imines or polyamide-amide.
The present invention compared with prior art has the following advantages and the high-lighting effect:
The big molecule grafting that will contain a large amount of amino can significantly improve the adsorption capacity of adsorbent to mycelium surface.Because mycelium surface contains amino and hydroxyl, acid chloride groups and the epoxide group in the epoxychloropropane in the chlorine acyl chlorides are easy to and its reaction, to contain the cl radical grafting at mycelium surface, contain amino big molecule and can arrive the cl radical generation substitution reaction of mycelium surface with grafting under given conditions, thereby mycelium surface is arrived in big molecule grafting.Owing to contain a large amount of amino and imido grpup in the big molecule, in water, can freely stretch, thereby, improve the adsorption capacity of adsorbent for pollutant provides numerous adsorption sites.
The isoelectric point of the ammonification adsorbent that modification obtains is the positively charged adsorbents in a kind of surface greater than pH 10.The used mycelium of the present invention is the mycelium pellet of diameter 3mm, is to be that the mycelium of 1.5 μ m is entwined mutually by diameter.The ESEM that passes through after the modification finds that the mycelium adsorbent surface after the modification is smooth, does not have tangible micropore, and mycelial diameter slightly increases (about 2 μ m).Utilize the zeta potential instrument to measure the surperficial zeta potential of modification front and back adsorbent, find that the isoelectric point of ammonifiers adosorbant is pH 10.2, apparently higher than promycelium (pH 3.8).Because the protonation of ammonification adsorbent surface amino, material surface is positively charged.This adsorbent pH less than 10.2 solution in surperficial positively charged, help the anionic pollutant in the adsorbed water.
The prepared ammonifiers adosorbant of the present invention has adsorbance height, characteristics such as reusable to typical incretion interferent.Ammonifiers adosorbant is to penta sodium pentachlorophenate electronegative in the water, 2, and 4-dichlorphenoxyacetic acid and PFOS have good adsorption effect, and with promycelium relatively, adsorbance improves 2.3～3.8 times.Adsorb saturated adsorbent and can adopt the sodium hydroxide solution of 0.1～1mol/L to soak 10 minutes, the amount ratio of NaOH regenerated liquid and adsorbent is 10-50mL/g, and is extremely neutral with big water gaging flushing then.The ammonification adsorbent is reused 10 times, to the not obviously decline of adsorbance of penta sodium pentachlorophenate.This adsorbent can be used to contain the industrial wastewater of high concentration anionic organic pollution, and the adsorbent after the absorption can be regenerated, and also can carry out burning disposal.Because mycelium is a biomaterial, biodegradation does not easily produce secondary pollution.
The specific embodiment
Mycelium among the present invention can be the discarded mycelium of fermentation industry, also can be the mycelium of laboratory cultures.The composition of the mycelial fluid nutrient medium of laboratory cultures is a 30g glucose, the 2g ammonium nitrate, and the 2g yeast extract, the 1g potassium dihydrogen phosphate, 0.5g epsom salt, 0.5g potassium chloride are dissolved in the 1000mL deionized water, and regulating the pH value is 5.5.Fluid nutrient medium is positioned in the conical flask of 250mL under the rotating speed of 140rpm, cultivates 3 days for 30 ℃, obtains the mycelium pellet of the about 3mm of diameter.
Concrete preparation method of the present invention is as follows:
With mycelium (Penicillium notatum or citric acid fungus) is raw material, and freeze drying is cleaned in mycelium sterilization back with deionized water; Dried mycelium is joined in chloroform or the dimethyl formamide organic solvent, the w/v of mycelium and organic solvent is 1～2.5g/100mL, dropwise add glue crosslinking agent (chloracetyl chloride, chlorpromazine chloride, chlorobutanoylchloride or epoxychloropropane) then, glue crosslinking agent and mycelial envelope-bulk to weight ratio are 0.5～4mL/g, after the seal of vessel at 25～100 ℃ down behind reaction 8～24h, filter mycelium, and clean with chloroform or dimethyl formamide organic solvent; The mycelium that obtains is put into chloroform or the solvent dimethylformamide that contains amino big molecule (polymine, polyethylene polyamine, diamine butane polypropylene imines or polyamide-amide), the w/v that contains amino big molecule and organic solvent is 5～20g/100mL, the w/v of mycelium and organic solvent is 0.5～2g/100mL, then at 80～100 ℃ of reaction 10～24h; Filtration obtains mycelium, uses earlier methyl alcohol, and the responseless reagent of mycelium surface is cleaned with deionized water in the back, obtains ammonifiers adosorbant, and freeze drying is to constant weight.
It is as follows to the experimental technique of incretion interferent adsorbance that the present invention measures adsorbent: add 100mL pollutant solution in the 250mL triangular flask, adjusting the initial pH of solution is 6, add the mycelium adsorbent then, add behind the bottle stopper in the constant temperature shaking table that triangular flask is placed on 15 ℃ with the rotating speed absorption of 120rpm 12 hours, use the membrane filtration of 0.45 μ m then, measure the content of residual contamination thing in the filtrate, calculate the adsorbance of mycelium adsorbent pollutant with following formula:
q＝(C
0-C
e)V/W
Wherein: q is adsorbance (mg/g); C
0Initial concentration (mg/L) for pollutant; C
eEquilibrium concentration (mg/L) for absorption after stain thing; V is liquor capacity (L); W is adsorbent weight (g).
Embodiment 1: 1g penicillium chrysogenum mycelium is joined in the 40mL solvent dimethylformamide, be added dropwise to the 4mL epoxychloropropane then, react 8h down at 100 ℃, filter, mycelium is put into the dimethyl formamide solution that 200mL contains polymine after cleaning with dimethyl formamide, the concentration of polymine is the 5g/100mL solvent dimethylformamide, 100 ℃ are reacted 24h down, filter the back and use earlier methyl alcohol, the responseless polymine of mycelium surface is cleaned with deionized water in the back, freeze drying obtains ammonifiers adosorbant to constant weight.0.05g ammonification adsorbent is put into the 250mL triangular flask, add the pentachlorophenol sodium solution that 100mL concentration is 200mg/L (pH=6) again, in rotating speed is the shaking table of 120rpm, adsorb 12h (reaching balance).The adsorbance that calculates ammonification adsorbents adsorb penta sodium pentachlorophenate is 323mg/g.
Embodiment 2: 0.2g citric acid fungus filament is put in the 20mL chloroform solvent, the chloracetyl chloride that dropwise adds 0.1mL then, after the seal of vessel at 25 ℃ down behind the reaction 24h, filter, change in the chloroformic solution of 10mL polyamide-amide after mycelium cleaned with chloroform, the concentration of polyamide-amide is the 20g/100mL chloroform solvent, and 80 ℃ are reacted 10h down.Filter the back and use earlier methyl alcohol, the back is with the deionized water unreacting reagent of clean mycelium surface repeatedly, and freeze drying obtains ammonifiers adosorbant to constant weight.The adsorbent of 0.05g preparation is put into the 250mL triangular flask, add the pentachlorophenol sodium solution that 100mL concentration is 200mg/L (pH=6) again, in rotating speed is the shaking table of 120rpm, adsorb 12h (reaching balance).The adsorbance that calculates ammonification adsorbents adsorb penta sodium pentachlorophenate is 289mg/g.
Embodiment 3: 0.2g penicillium chrysogenum mycelium is put in the 20mL chloroform solvent, the chloracetyl chloride that dropwise adds 0.1mL then, after the seal of vessel at 25 ℃ down behind the reaction 24h, filter, change in the chloroformic solution of 50mL polyethylene polyamine after mycelium cleaned with chloroform, the concentration of polyethylene polyamine is the 20g/100mL chloroform solvent, and 100 ℃ are reacted 24h down.Filter the back and use earlier methyl alcohol, the back is with the deionized water unreacting reagent of clean mycelium surface repeatedly, and freeze drying obtains ammonifiers adosorbant to constant weight.The adsorbent of 0.05g preparation is put into the 250mL triangular flask, and adding 100mL concentration again is 200
The pentachlorophenol sodium solution of mg/L (pH=6) adsorbs 12h (reaching balance) in rotating speed is the shaking table of 120rpm.The adsorbance that calculates ammonification adsorbents adsorb penta sodium pentachlorophenate is 235mg/g.
Embodiment 4: 0.25g penicillium chrysogenum mycelium is put in the 15mL chloroform solvent, the chloracetyl chloride that dropwise adds 0.4mL then, after the seal of vessel at 25 ℃ down behind the reaction 8h, filter, change in the dimethyl formamide solution of polymine of 50mL10% 100 ℃ of reaction 24h down after mycelium cleaned with chloroform over to.Filter the back and use earlier methyl alcohol, the back is with the deionized water unreacting reagent of clean mycelium surface repeatedly, and freeze drying obtains ammonifiers adosorbant to constant weight.
The ammonification adsorbents adsorb penta sodium pentachlorophenate that utilizes example 4 to obtain, the initial concentration of penta sodium pentachlorophenate is 300mg/L, and the initial pH=6 of solution, the consumption of adsorbent are 0.02g/100mL, and adsorption time is 12h.The concentration of pentachlorophenol is measured at the 320nm place with ultraviolet specrophotometer (Agilent 8453, Germany) in the solution of absorption back.Experimental result shows that the adsorbance of ammonification adsorbent reaches 347mg/g, and promycelium adsorbance under the same conditions is 73mg/g.As seen, the adsorbance of adsorbent has increased by 3.8 times after the modification.
The ammonification adsorbents adsorb 2 of utilizing example 4 to obtain, the 4-dichlorphenoxyacetic acid, 2, the initial concentration of 4-dichlorphenoxyacetic acid is 235
Mg/L, the initial pH=6 of solution, the consumption of adsorbent are 0.02g/100mL, adsorption time is 12h.In the solution of absorption back 2, the concentration of 4-D is measured at the 283nm place with ultraviolet specrophotometer (Agilent 8453, Germany).Result of the test shows that the adsorbance of ammonification adsorbent reaches 182mg/g, and the adsorbance of promycelium is 52mg/g.As seen, the adsorbance of adsorbent has increased by 2.5 times after the modification.
The ammonification adsorbents adsorb PFOS potassium that utilizes example 4 to obtain, PFOS potassium initial concentration is 400mg/L, the initial pH of solution is adjusted into 6, the consumption of adsorbent is 0.02g/100mL, adsorb reached adsorption equilibrium in 12 hours after, measure the content of residue PFOS potassium in the filtrate with HPLC.Experimental result shows that the ammonifiers adosorbant of modification reaches 1034mg/g to the adsorbance of PFOS potassium, and the adsorbance of promycelium is 315mg/g.As seen, the adsorbance of adsorbent has increased by 2.3 times after the modification.
Claims (3)
1. the preparation method of an ammonifiers adosorbant is characterized in that this method carries out as follows:
1) with the mycelium is raw material, mycelium sterilization back is cleaned with deionized water, be stored in the drier standby after the freeze drying;
2) dried mycelium is joined in chloroform or the dimethyl formamide organic solvent, the w/v of mycelium and organic solvent is 1～2.5g/100mL, dropwise add glue crosslinking agent then, glue crosslinking agent and mycelial envelope-bulk to weight ratio are 0.5～4mL/g, after the seal of vessel at 25～100 ℃ down behind reaction 8～24h, filter mycelium, and clean with chloroform or dimethyl formamide organic solvent; Used glue crosslinking agent is chloracetyl chloride, chlorpromazine chloride, chlorobutanoylchloride or epoxychloropropane;
3) with step 2) mycelium that obtains puts into and contains amino macromolecular chloroform or solvent dimethylformamide, the described w/v that contains amino big molecule and organic solvent is 5～20g/100mL, the w/v of mycelium and organic solvent is 0.5～2g/100mL, then at 80～100 ℃ of reaction 10～24h; Filtration obtains mycelium, uses earlier methyl alcohol, and the responseless reagent of mycelium surface is cleaned with deionized water in the back, obtains ammonifiers adosorbant, and freeze drying is to constant weight.
2. the preparation method of a kind of ammonifiers adosorbant according to claim 1, it is characterized in that: used mycelium is Penicillium notatum or citric acid fungus mycelium.
3. the preparation method of a kind of ammonifiers adosorbant according to claim 1 is characterized in that: used to contain amino big molecule be polymine, polyethylene polyamine, diamine butane polypropylene imines or polyamide-amide.
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| CN101574642B (en) * | 2009-06-09 | 2011-05-25 | 厦门大学 | Preparation method of biological sorbent used for treating phthalocyanines dye waste water |
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| CN103285835B (en) * | 2013-05-31 | 2015-12-09 | 西安科技大学 | A kind of nanometer Fe 0the preparation method of/polymine association complex |
| CN103252221B (en) * | 2013-05-31 | 2015-10-14 | 西安科技大学 | A kind of nanometer Fe 0the preparation method of/polyethylene polyamine association complex |
| CN104860369B (en) * | 2015-04-22 | 2016-09-07 | 苏州大学 | A kind of method utilizing Penicillium notatum absorption to reclaim the triclosan in sewage |
| CN105462899B (en) * | 2015-12-23 | 2018-08-07 | 江南大学 | It is a kind of that there is the lactobacillus plantarum for alleviating PFOS murder by poisoning functions and its application |
| CN110404517A (en) * | 2019-08-15 | 2019-11-05 | 中国科学院长春应用化学研究所 | A kind of polyvinyl alcohol based porous adsorbing material and preparation method thereof |
| CN112225326A (en) * | 2020-09-30 | 2021-01-15 | 中国科学院天津工业生物技术研究所 | Application of mycelium material in oil absorption |
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