CN117732432A - Biochar aerogel loaded pyrite composite material and preparation method and application thereof - Google Patents
Biochar aerogel loaded pyrite composite material and preparation method and application thereof Download PDFInfo
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- CN117732432A CN117732432A CN202311814759.9A CN202311814759A CN117732432A CN 117732432 A CN117732432 A CN 117732432A CN 202311814759 A CN202311814759 A CN 202311814759A CN 117732432 A CN117732432 A CN 117732432A
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- Prior art keywords
- biochar
- aerogel
- tce
- pyrite
- composite material
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- 239000004964 aerogel Substances 0.000 title claims abstract description 101
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 91
- 239000011028 pyrite Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 74
- 230000015556 catabolic process Effects 0.000 claims abstract description 64
- 239000006285 cell suspension Substances 0.000 claims abstract description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 244000005700 microbiome Species 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229930003268 Vitamin C Natural products 0.000 claims abstract description 8
- 235000019154 vitamin C Nutrition 0.000 claims abstract description 8
- 239000011718 vitamin C Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 145
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 139
- 238000000034 method Methods 0.000 claims description 21
- 239000006228 supernatant Substances 0.000 claims description 15
- 239000002609 medium Substances 0.000 claims description 14
- 239000001963 growth medium Substances 0.000 claims description 13
- 230000000813 microbial effect Effects 0.000 claims description 13
- 239000002689 soil Substances 0.000 claims description 10
- 241000589516 Pseudomonas Species 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 230000002195 synergetic effect Effects 0.000 claims description 8
- 230000000593 degrading effect Effects 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 6
- 238000012258 culturing Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 241000193403 Clostridium Species 0.000 claims description 3
- 241000589519 Comamonas Species 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000003698 anagen phase Effects 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 41
- 239000003463 adsorbent Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 150000001447 alkali salts Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229930003231 vitamin Natural products 0.000 description 4
- 235000013343 vitamin Nutrition 0.000 description 4
- 239000011782 vitamin Substances 0.000 description 4
- 229940088594 vitamin Drugs 0.000 description 4
- 150000003722 vitamin derivatives Chemical class 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002504 physiological saline solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- KFUSEUYYWQURPO-UPHRSURJSA-N cis-1,2-dichloroethene Chemical group Cl\C=C/Cl KFUSEUYYWQURPO-UPHRSURJSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 1
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 1
- GHOKWGTUZJEAQD-SSDOTTSWSA-N 3-[[(2s)-2,4-dihydroxy-3,3-dimethylbutanoyl]amino]propanoic acid Chemical compound OCC(C)(C)[C@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-SSDOTTSWSA-N 0.000 description 1
- 241001655514 Anaerobacterium Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000626621 Geobacillus Species 0.000 description 1
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- PLXBWHJQWKZRKG-UHFFFAOYSA-N Resazurin Chemical compound C1=CC(=O)C=C2OC3=CC(O)=CC=C3[N+]([O-])=C21 PLXBWHJQWKZRKG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
- 241000605118 Thiobacillus Species 0.000 description 1
- 241001645838 Thiospira Species 0.000 description 1
- 229930003779 Vitamin B12 Natural products 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- SNPLKNRPJHDVJA-UHFFFAOYSA-N dl-panthenol Chemical compound OCC(C)(C)C(O)C(=O)NCCCO SNPLKNRPJHDVJA-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229960000304 folic acid Drugs 0.000 description 1
- 235000019152 folic acid Nutrition 0.000 description 1
- 239000011724 folic acid Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- ZUFQODAHGAHPFQ-UHFFFAOYSA-N pyridoxine hydrochloride Chemical compound Cl.CC1=NC=C(CO)C(CO)=C1O ZUFQODAHGAHPFQ-UHFFFAOYSA-N 0.000 description 1
- 229960004172 pyridoxine hydrochloride Drugs 0.000 description 1
- 235000019171 pyridoxine hydrochloride Nutrition 0.000 description 1
- 239000011764 pyridoxine hydrochloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006042 reductive dechlorination reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 229960002477 riboflavin Drugs 0.000 description 1
- 235000019192 riboflavin Nutrition 0.000 description 1
- 239000002151 riboflavin Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride 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
- 235000019157 thiamine Nutrition 0.000 description 1
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- 235000019163 vitamin B12 Nutrition 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention discloses a biochar aerogel supported pyrite composite material, a preparation method and application thereof, and the preparation method of the biochar aerogel supported pyrite composite material comprises the following steps: mixing pyrite, biochar aerogel, zero-valent iron and water, carrying out ultrasonic treatment until the mixture is uniformly dispersed to obtain a first solution, mixing vitamin C and the first solution, standing at 60-65 ℃ for reaction for 12-12.5 h, washing, and drying to obtain the biochar aerogel-loaded pyrite composite material, wherein the addition of the biochar aerogel-loaded pyrite composite material can regulate and control the community structure of microorganisms in DM cell suspension, so that the degradation capacity to TCE is improved, the DM cell suspension and the biochar aerogel-loaded pyrite composite material are simultaneously added, and the degradation rate to TCE when the DM cell suspension is added after the biochar aerogel-loaded pyrite composite material is respectively higher than that when the DM cell suspension is singly added, thereby improving 1.77-2.76 times.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a biochar aerogel loaded pyrite composite material, and a preparation method and application thereof.
Background
Chlorinated organic compounds, such as polychlorinated biphenyls, hexachlorobenzene, perchloroethylene and Trichloroethylene (TCE), are common in pesticides and industrial cleaning solutions. TCE is one of the most widely distributed chlorinated organics in aquatic environments, and has the polluting properties of volatility, toxicity, concealment, accumulation and diversity. It can severely threaten public health and ecosystems. TCE is widely used in the fields of machinery, chemistry, medicine and the like, and often enters soil and water environment through unreasonable discharge of industrial wastewater and domestic sewage, waste accumulation, site leakage, toxic and harmful chemical leakage and the like, so that TCE becomes one of the most common soil organic pollutants.
Biodegradation is considered a promising technique for in situ remediation of contaminated groundwater and soil. However, due to the restriction of underground environment factors, the indigenous functional microorganisms in the soil often have the problems of insufficient quantity, low activity, slow growth and the like, so that the natural attenuation effect of organic pollutants is poor. Studies have shown that functional microbial degradation plays a dominant role in the natural decay of organic contaminants. Part of the Organic Halide Respiratory Bacteria (OHRB) are capable of reductive dechlorination of TCE. OHRB includes anaerobacterium, thiobacillus, thiospira, geobacillus, and the like, and is widely found in various environments such as soil, sediment, and aquifer. However, the degradation of TCE by microorganisms alone also suffers from the problems of low degradation efficiency, long period, susceptibility of microorganisms to toxicity limitation and inactivation of TCE at high concentrations, inability to achieve complete degradation of TCE, resulting in accumulation of the more toxic intermediate product, vinyl chloride, and the like. Therefore, how to enhance the efficacy of microbial degradation of TCE is critical to achieving low carbon repair.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a biochar aerogel loaded pyrite composite material.
The invention also aims to provide the biochar aerogel loaded pyrite composite material obtained by the preparation method.
The invention also aims to provide an application of the biochar aerogel-loaded pyrite composite material and a microorganism in the synergistic degradation of trichloroethylene, wherein the biochar aerogel-loaded pyrite composite material is used as a chemical reduction adsorbent, and the microorganism is used as a biodegradation agent, and the biochar aerogel-loaded pyrite composite material and the microorganism act synergistically. Zero-valent iron in the biochar aerogel-loaded pyrite composite material accelerates the degradation rate of trichloroethylene, and the biochar aerogel in the biochar aerogel-loaded pyrite composite material provides a growing environment and nutrient substances for microorganisms.
The aim of the invention is achieved by the following technical scheme.
The preparation method of the biochar aerogel loaded pyrite composite material comprises the following steps:
step 1, pyrite (FeS) 2 ) Biochar aerogel (CA), zero valent iron (Fe 0 ) Mixing with water, and ultrasonic dispersing to obtain a first solution, wherein pyrite (FeS 2 ) The ratio of the biochar aerogel (CA) to the zero-valent iron is (0.5-1.5): (0.5-2): (0-1);
in the step 1, the ratio of the mass parts of the biochar aerogel (CA) to the volume parts of the water in the step 1 is (0.5-1): (20-25), wherein the unit of the mass fraction is g, and the unit of the volume fraction is mL.
In the step 1, the ultrasonic time is 30-40 min.
In step 1, pyrite (FeS 2 ) The ratio of biochar aerogel (CA) to zero-valent iron is preferably (0.5-1): (1-2): (0.5-1).
Step 2, mixing vitamin C and the first solution, standing at 60-65 ℃ for reaction for 12-12.5 h, washing and drying to obtain the biochar aerogel supported pyrite composite material, wherein the ratio of the vitamin C to the biochar aerogel (CA) is (2.5-5) in parts by weight: (0.5-1).
In step 2, the washing uses ethanol.
In step 2, the drying is performed under vacuum.
In the step 2, the drying is freeze drying, and the drying time is 20-24 hours.
In the above technical scheme, the pyrite (FeS 2 ) Is powder with the particle size of 1-100 nm.
In the above technical scheme, the method for preparing the biochar aerogel (CA) specifically comprises the following steps: KOH, NH 4 Cl、Na 2 S·9H 2 Mixing O and water, stirring to be uniform to obtain a solution A, mixing rhamnolipid and the solution A, stirring and reacting for 2-2.5 hours at 0-5 ℃, drying to obtain a biochar aerogel precursor, carbonizing the biochar aerogel precursor for 2-2.5 hours at 800-805 ℃ under nitrogen atmosphere, and cleaning to be neutral to obtain the biochar aerogel (CA), wherein the KOH and NH are calculated according to parts by weight 4 Cl and Na 2 S·9H 2 The ratio of O is (1-2): (2-4): (1-2), wherein the ratio of KOH to rhamnolipid is (6.25-12.5) in parts by weight: (5-10).
In the method of preparing a biochar aerogel (CA), the drying is freeze drying.
In the method for preparing the biochar aerogel (CA), the ratio of the mass parts of KOH to the volume parts of water is (6.25-12.5): (20-40), wherein the unit of the mass parts is g, and the unit of the volume parts is mL.
In the method for preparing the biochar aerogel (CA), water is used for cleaning.
The biochar aerogel loaded pyrite composite material obtained by the technical scheme.
The application of the biochar aerogel loaded pyrite composite material in the synergistic degradation of trichloroethylene by microorganisms.
In the technical scheme, the method for degrading trichloroethylene by the synergistic effect of the biochar aerogel loaded pyrite composite material and microorganisms comprises the following steps: adding the biochar aerogel loaded pyrite composite material and DM cell suspension into a solution to be degraded containing TCE for degradation, wherein the DM cell suspension is a microorganism suspension, the DM cell suspension is added so that the OD value of cells at 600nm in the solution to be degraded is 0.1-0.5, and the DM cell suspension comprises the following microorganisms in number: 10 to 20 percent of pseudomonas, 30 to 40 percent of clostridium, 20 to 40 percent of pseudomonas and 5 to 20 percent of comamonas.
In the technical scheme, the biochar aerogel loaded pyrite composite material is firstly added into the liquid to be degraded, and is kept stand for at least 24 hours, then DM cell suspension is added, and degradation is carried out under anaerobic and dark conditions.
In the above technical scheme, the OD value of the DM cell suspension at 600nm is 1.1-1.3.
In the technical scheme, the temperature of the biochar aerogel loaded pyrite composite material and the temperature of the synergistic degradation of the trichloroethylene by microorganisms are 25-30 ℃.
In the technical scheme, after the biochar aerogel loaded pyrite composite material is added, the concentration of the biochar aerogel loaded pyrite composite material in the degradation liquid is 0.01-1.0 g/L.
In the above technical solution, the method for obtaining DM cell suspension comprises: soaking soil polluted by chlorinated hydrocarbon in normal saline for at least 12 hours, and carrying out domestication in a culture medium with gradually increased TCE concentration to obtain microbial flora, carrying out suspension treatment on the microbial flora by using the culture medium, centrifuging in a logarithmic growth phase, discarding supernatant, washing by using sterilized normal saline, and storing in the sterilized normal saline to obtain DM cell suspension, wherein the domestication comprises the following steps of repeatedly: taking supernatant into a culture medium containing TCE, and culturing for 3-10 days in an anaerobic environment.
In the technical scheme, the concentration of TCE in the culture medium adopted by the domestication is 10-50 mg/L.
In the technical scheme, the ratio of the supernatant to the culture medium containing TCE is 1 (1-15) in parts by volume.
In the above technical scheme, the medium is a basal salt medium (MSM).
In the above technical scheme, before the basal salt medium (MSM) is used, a vitamin solution is added into the basal salt medium (MSM).
Compared with the prior art, the invention has the beneficial effects that:
1. trichloroethylene (TCE) can be degraded by microorganisms or by biochar aerogel-loaded pyrite composite materials, but the biochar aerogel-loaded pyrite composite materials and microorganisms are degraded cooperatively, so that the addition of the biochar aerogel-loaded pyrite composite materials can regulate and control the community structure of microorganisms in DM cell suspension, the degradation capacity to TCE is improved, the DM cell suspension and the biochar aerogel-loaded pyrite composite materials are added simultaneously, and the degradation rate to TCE after the biochar aerogel-loaded pyrite composite materials is added is higher than that of the DM cell suspension which is added independently, so that the degradation rate is improved by 1.77-2.76 times;
2. the preparation method of the biochar aerogel supported pyrite composite material is simple, and pyrite and zero-valent iron (Fe) are reduced by ultrasonic and standing vitamin C methods 0 ) Fixing on biochar aerogel;
3. the DM cell suspension has high adaptability to the environment, and can obtain better degradation efficiency under the condition of smaller addition amount without adding nutrient substances.
4. The degradation step of adding the biochar aerogel loaded pyrite composite material into the liquid to be degraded and then adding the DM cell suspension can realize thorough degradation of TCE.
Drawings
FIG. 1 is a graph showing the abundance of microorganisms (T0 is the colony structure of microorganisms in DM cell suspension of example 1, T1 is the concentration of microorganisms in DM cell suspension and FeS) 2 -Fe 0 Microbial community structure after @ CA co-treatment);
FIG. 2 is a graph showing the trend of the effect of the concentration of different DM cell suspensions on the TCE degradation rate;
FIG. 3 shows the TCE removal effect of examples 4 to 7;
FIG. 4 is pyrite FeS 2 And FeS 2 -Fe 0 FTIR graphs of @ CA composite
FIG. 5 shows the degradation rate of TCE for examples 14-19;
FIG. 6 is FeS 2 -Fe 0 Effect of @ CA concentration on the degradation rate of TCE;
FIG. 7 is a trend graph of TCE removal effect for examples 3, 14, 20, 15, 21, 19 and 22;
FIG. 8 is a graph showing the trend of the addition sequence of the adsorbent and DM cell suspension (examples 20-28) with respect to the effect of TCE removal.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The raw materials and purchase sources involved in the following examples are as follows:
the instruments and models involved in the following examples are as follows:
planetary ball mill: F-P2000, hunan French laboratory instruments, inc., changsha, china;
anaerobic incubator: HYQX-II, shanghai, medical instruments Inc., shanghai, china.
The water in the examples described below is deionized water, unless otherwise specified.
Degradation rate = (pre-reaction TCE concentration-post-reaction TCE concentration)/pre-reaction TCE concentration in the following examples, the concentration of TCE in the supernatant after the end of the experiment was the post-reaction TCE concentration, and the pre-reaction TCE concentration was 30mg/L.
The dark resting anaerobic reaction in the following examples is: the headspace bottle was sealed with a lid containing a polytetrafluoroethylene gasket, and the headspace bottle was placed in an anaerobic incubator for reaction at 30 ℃. After the reaction, the headspace bottle was taken out of the anaerobic tank.
Example 1
Extracting microbial flora from soil polluted by chlorinated hydrocarbon to obtain DM cell suspension with high degradation rate of TCE.
A method of preparing a DM cell suspension comprising: adding 5g of chlorinated hydrocarbon contaminated soil (the chlorinated hydrocarbon contaminated soil is taken from a chlorinated hydrocarbon contaminated repair pilot plant base in North Chen district of Hebei university of industry) into 50mL of brown bottle 1, adding 30mL of physiological saline, soaking for 24h at room temperature, adding 27mL of basic salt culture medium (MSM) containing 10mg/LTCE into another 50mL of brown bottle 2, adding the supernatant in 3mL of brown bottle 1 into brown bottle 2, sealing brown bottle 2 with a cover of a polytetrafluoroethylene gasket, and culturing for 7d in an anaerobic tank to obtain a first culture solution;
taking another 50mL brown bottle 3, adding 27mL of basic salt culture medium (MSM) containing 20mg/L TCE, taking 3mL of first culture solution, adding the first culture solution into the brown bottle 3, sealing the brown bottle 3 by using a cover of a polytetrafluoroethylene gasket, and culturing for 7d in an anaerobic box to obtain a second culture solution;
taking another 50mL brown bottle 4, adding 27mL of basic salt culture medium (MSM) containing 30mg/L TCE, taking 3mL of second culture solution, adding the second culture solution into the brown bottle 4, sealing the brown bottle 4 by using a cover of a polytetrafluoroethylene gasket, and culturing for 7d in an anaerobic box to obtain a third culture solution;
taking another 50mL brown bottle 5, adding 27mL of basic salt culture medium (MSM) containing 40mg/L TCE, adding 3mL of third culture solution into the brown bottle 5, sealing the brown bottle 5 by using a cover of a polytetrafluoroethylene gasket, and culturing for 7d in an anaerobic box to obtain a fourth culture solution;
another 50mL brown flask 6 was taken, 27mL of a basic salt medium (MSM) containing 50mg/L TCE was added, 3mL of a fourth culture solution was added to the brown flask 6, the brown flask 6 was sealed with a cover made of a polytetrafluoroethylene gasket, and cultured in an anaerobic tank for 7d to obtain a fifth culture solution.
Centrifuging the fifth culture solution at 8000rpm for 10min to obtain microbial flora. The microbial flora was subjected to suspension treatment using basic salt medium (MSM), centrifuged at 8000rpm at 4℃for 10min during the logarithmic phase of growth, the supernatant was discarded, washed 3 times with sterilized physiological saline, and stored in 5mL of sterilized physiological saline to give DM cell suspension having a cell OD at 600nm of 1.2. The microorganisms in the DM cell suspension are counted as indicated in column T0 of fig. 1, and include: 19% Pseudomonas, 37.5% Clostridium, 31.5% Pseudomonas and 10.7% Comamonas.
Basic salt medium (MSM) includes: basic mineral salt culture medium (BMM) 10%v/v, 1%v/v trace mineral solution, 0.25mL/L resazurin, 2.292g/L Tri-ethanesulfonic acid, 0.048g/L Na 2 S·9H 2 O, 0.242g/L L-cysteine, 0.0771g/L DL-panthenol, 2.52g/L NaHCO 3 And water as a solvent.
Basic mineral salt medium (BMM) includes: 1g/L NaCl, 0.2g/L KH 2 PO 4 、0.5g/L MgCl 2 ·6H 2 O、0.3g/L NH 4 Cl、0.3g/L KCl、0.015g/L CaCl 2 ·2H 2 O and water.
The trace mineral solution includes: 1.5g/L FeCl 2 ·4H 2 O、0.1g/L CoCl 2 ·6H 2 O、0.07g/L ZnCl 2 、0.006g/L H 3 BO 3 、0.036g/L NaMoO 4 ·2H 2 O、0.024g/L NiCl 2 ·6H 2 O、0.02g/L CuCl 2 ·2H 2 O and water.
The pH of the basal salt medium (MSM) was 7.4. Before using the basal salt medium (MSM), a vitamin solution was added to the basal salt medium (MSM), 0.1mL of the vitamin solution was added per 50mL of the basal salt medium (MSM), and the mixture was sterilized in an autoclave at 121℃for 30 minutes after the addition, thereby obtaining the DM cell suspension. Wherein the vitamin solution comprises: 0.02mg/L biotin, 0.02mg/L folic acid, 0.1mg/L pyridoxine hydrochloride, 0.05mg/L riboflavin, 0.05mg/L thiamine, 0.05mg/L niacin, 0.05mg/L pantothenic acid, 0.05mg/L para-aminobenzoic acid, 0.001mg/L vitamin B12, and water.
Example 2
Different volumes of the DM cell suspension obtained in example 1 were centrifuged, and after centrifugation, mixed with basal salt medium (MSM) to a volume of 0.7mL to obtain DM cell sap.
A method of TCE degradation comprising: adding TCE water solution with concentration of 7mLTCE of 30mg/L into a 20mL headspace bottle, and introducing ultrapure N 2 To drive off oxygen, 0.7mL DM cell fluid was added again to make the OD value of the cell at 600nm 0.0375, 0.075, 0.1125, 0.15, 0.30 or 0.45, adjusted to ph=8.0, and the reaction was allowed to stand in darkness for anaerobic reaction for 48 hours at 30 ℃, the concentration of TCE in the supernatant was analyzed, and the degradation rate of TCE was calculated.
As shown in fig. 2, by adjusting the different OD values, it was found that the degradation rate of TCE increased with increasing OD value from 6% to 31% during the increase of OD value from 0.0375 to 0.15. This is probably due to the increased number of added microorganisms, increased dechlorination enzymes produced by the microorganisms and increased degradation rates of TCE. At OD values above 0.15, the degradation rate of TCE did not increase, or even decreased slightly. This is because, when the concentration of the microorganism exceeds the optimum concentration, the enzymes secreted by the microorganism cannot be used completely effectively, resulting in no longer increasing the degradation rate. Meanwhile, due to limited nutrients, nutrient competition exists among microorganisms, and growth and propagation of microorganisms are inhibited, so that degradation efficiency is not increased.
Example 3
A method of TCE degradation comprising: adding TCE water solution with concentration of 7mLTCE of 30mg/L into a 20mL headspace bottle, and introducing ultrapure N 2 To drive off oxygen, 0.7mL of DM cell suspension from example 1 was added to bring the OD of the cell at 600nm to 0.15, adjusted to ph=8.0, and the headspace was sealed with a cap containing a teflon gasket to ensure that the experiment was performed in anaerobic conditions. The headspace bottle is placed in an anaerobic incubator for anaerobic reaction for 48 hours in a dark standing state, and the reaction temperature is 30 ℃. After the experiment is finished, the headspace bottle is taken out of the anaerobic box, the concentration of TCE in the supernatant is analyzed, and the degradation rate of TCE is calculated.
Example 4
A TCE degradation process substantially the same as example 3, with the only difference that: the TCE aqueous solution is a mixture of TCE and lake water (lake water is taken from the university of Hebei industries).
Example 5
A TCE degradation process substantially the same as example 3, with the only difference that: the TCE aqueous solution is a mixture of TCE and sterilized lake water (lake water is taken from the university of Hebei Industrial, sterilization: the lake water is kept at 121 ℃ for 30 minutes).
Example 6
A TCE degradation process was essentially the same as example 4, with the only difference that: the aqueous TCE solution also contains 10mg/L of chromium sulfate.
Example 7
A TCE degradation process was essentially the same as example 4, with the only difference that: the aqueous TCE solution also contains 10mg/L benzoquinone.
The degradation rate of TCE after the reaction of examples 4 to 7 was completed is shown in FIG. 3. It can be seen from examples 4 and 5 that no interference is generated to the ability of DM cell suspensions to degrade TCE (degradation rate is maintained at about 31%) regardless of whether the actual water (lake water) is sterilized, indicating that microorganisms present in the actual water do not affect the degradation ability of DM cell suspensions. Meanwhile, it can be seen from examples 6 and 7 that the ability of DM cell suspensions to degrade TCE was not significantly disturbed when chromium sulfate or benzoquinone were present (wherein the presence of chromium sulfate slightly reduced the TCE degradation rate from 31% to 27.5%). Overall, DM cell suspensions are relatively stable in their ability to degrade TCE, which facilitates their subsequent application in practically contaminated sites.
Example 8
Pyrite (FeS) 2 ) The preparation method of (2) comprises the following steps: ultrasonic treatment (20 kHz) of natural pyrite particles for 1h to remove impurities, placing 1.5g of the ultrasonic natural pyrite particles in a 500mL zirconia ball mill tank, adding zirconia balls (according to mass ratio, large balls)Middle ball->Ball with ball shapeIs added in a ratio of (2) such that the mass ratio of natural pyrite particles to zirconia balls is 1:100, introducing 30min N into a zirconia ball milling tank 2 (>99 percent), then putting the sealed zirconia ball milling tank into a planetary ball mill, ball milling for 2 hours at the room temperature at the rotating speed of 600rpm to obtain pyrite precursor (powder), flushing with ethanol and deionized water for three times to remove impurities, and finally drying for 3 hours at the temperature of 105 ℃ to obtain pyrite, wherein the pyrite is powder with the particle size of 1-100 nm through testing.
Example 9
A method of preparing a biochar aerogel (CA) comprising: KOH, NH 4 Cl and Na 2 S·9H 2 O (in parts by weight, KOH, NH) 4 Cl and Na 2 S·9H 2 The ratio of O is 1:2:1, KOH, NH 4 Cl and Na 2 S·9H 2 The mass sum of O is 25 g) is dissolved in 20mL of water, the mixture is stirred uniformly to obtain a solution A, the solution A and 5g of rhamnolipid are mixed, the mixture is stirred for 2h (stirring reaction) at 0 ℃, the mixture is freeze-dried to form aerogel, a biochar aerogel precursor is obtained, and the biochar aerogel precursor is placed in a tube furnace for carbonization: under vacuum, raising the temperature to 800 ℃ at a rate of 5 ℃/min, and N at 800 DEG C 2 Flowing down, staying in the tube furnace for 2 hours, thoroughly flushing with deionized water for several times, removing unreacted reagent, and washing to be neutral to obtain the biochar aerogel (CA).
Examples 10 to 13
The preparation method of the biochar aerogel loaded pyrite composite material comprises the following steps:
step 1, pyrite (FeS) obtained in example 8 2 ) Biochar aerogel (CA) obtained in example 9, zero valent iron (Fe 0 ) Mixing with water, and ultrasonic dispersing for 30min to obtain a first solution, wherein pyrite (FeS) 2 ) Biochar aerogel (CA) and zero valent iron (Fe) 0 ) The sum of the masses of (2 g), in parts by mass, pyrite (FeS 2 ) Biochar aerogel (CA) and zero valent iron (Fe) 0 ) The ratio of the mass parts of the biochar aerogel (CA) to the volume parts of the water in the step 1 is Y, the unit of the mass parts is g, and the unit of the volume parts is mL;
and 2, mixing the vitamin C and the first solution, standing at 60 ℃ for reaction for 12 hours, washing with ethanol to remove impurities, and freeze-drying under vacuum for 24 hours to obtain the biochar aerogel-loaded pyrite composite material, wherein the ratio of the vitamin C to the biochar aerogel (CA) is Z in parts by weight.
| Examples | X | Y | Z | Numbering device |
| Example 10 | 1.5：0.5：0 | 0.5：20 | 2.5：0.5 | FeS 2 @CA |
| Example 11 | 0.75：0.5：0.75 | 0.5：20 | 2.5：0.5 | FeS 2 -Fe 0 @CA |
| Example 12 | 1：1：0 | 1：20 | 5：1 | FeS 2 @CA |
| Example 13 | 0.5：1：0.5 | 1：20 | 5：1 | FeS 2 -Fe 0 @CA |
Selection of pyrite (FeS) obtained in example 8 2 ) And the biochar aerogel loaded pyrite composite material of example 13 is characterized by surface functional groups, as shown in fig. 4, the single pyrite has fewer surface functional groups, mainly c=c, and has weaker adsorption capacity on TCE; after the composite material is compounded with the biochar aerogel, the types and the strength of functional groups on the surface of the biochar aerogel-loaded pyrite composite material are obviously improved, for example, the appearance and the strength of-COOH and C-O-C are improved, and the adsorption of TCE by the composite material is facilitated.
Examples 14 to 19
A method of TCE degradation comprising: adding TCE water solution with concentration of 7mLTCE of 30mg/L into a 20mL headspace bottle, and introducing ultrapure N 2 To drive off oxygen and then adding the adsorbent so that the concentration of the adsorbent in the TCE aqueous solution is 0.5g/L, sealing the headspace bottle with a cover containing a polytetrafluoroethylene gasket, and ensuring that all experiments are performed in anaerobic conditions. The headspace bottle is placed in an anaerobic incubator for anaerobic reaction for 48 hours in a dark standing state, and the reaction temperature is 30 ℃. After the experiment was completed, the headspace bottle was removed from the anaerobic tank and the supernatant was analyzed for TCE concentration. The adsorbent is one of pyrite prepared in example 8, biochar aerogel (CA) prepared in example 9 and biochar aerogel-loaded pyrite composite materials prepared in examples 10-13.
| Examples | Adsorbent and process for producing the same |
| Example 14 | Example 8 |
| Example 15 | Example 9 |
| Example 16 | Example 10 |
| Example 17 | Example 11 |
| Example 18 | Example 12 |
| Example 19 | Example 13 |
The characterization of the surface functional groups after the reaction of the biochar aerogel supported pyrite composite in example 19 is shown in fig. 4.
As shown in fig. 5, example 19 has a higher degradation rate of TCE than example 14. Because the biochar aerogel (CA) can well mix FeS 2 And Fe (Fe) 0 Dispersing FeS 2 -Fe 0 The @ CA possesses a larger specific surface area and more adsorption sites. At the same time, feS can be increased 2 And Fe (Fe) 0 Solubility in water. FeS (FeS) 2 And Fe (Fe) 0 After being compounded with the biochar aerogel, feS is added along with the increase of the adding proportion of the biochar aerogel 2 -Fe 0 The degradation rate of the @ CA to the TCE is continuously improved, which proves that increasing the proportion of the biochar aerogel is more beneficial to FeS 2 And Fe (Fe) 0 And (3) the separation and activity of the TCE are improved, so that the TCE is efficiently degraded.
The above experimental results show that the FeS prepared in example 13 2 -Fe 0 The best removal of TCE by @ CA, therefore the FeS prepared in example 13 was chosen 2 -Fe 0 CA was used for the next study.
Investigation of FeS 2 -Fe 0 Effect of @ CA concentration on TCE removal effect. Experimental conditions: adding TCE water solution with concentration of 7mLTCE of 30mg/L into a 20mL headspace bottle, and introducing ultrapure N 2 The oxygen was removed and then an adsorbent was added, the adsorbent being the FeS prepared in example 13 2 -Fe 0 The concentration of adsorbent in TCE aqueous solution was one of 0.01, 0.02, 0.05, 0.1, 0.3, 0.5 and 1g/L and the headspace vial was sealed with a cap containing a polytetrafluoroethylene gasket to ensure that all experiments were performed in anaerobic conditions. The headspace bottle is placed in an anaerobic incubator for anaerobic reaction for 7 days in a dark standing state, and the reaction temperature is 30 ℃. After the experiment was completed, the headspace bottle was taken out of the anaerobic tank, the concentration of TCE in the supernatant was analyzed, the degradation rate of TCE was calculated, and the test result was shown in fig. 6. It can be seen that FeS is increased 2 -Fe 0 The concentration of @ CA can obviously improve the degradation capability of the material to TCE, and the degradation capability of the material is along with FeS 2 -Fe 0 The concentration of @ CA is increased from 0.01 to 0.5g/L, and the degradation rate of TCE is increased from 25% to 73.1%, but when the concentration is increased to 1g/L again, the degradation rate of TCE is not increased. Combining with the limitation of microorganism degradation of TCE, the material is combined with microorganism, and the degradation capability of TCE is improved.
Example 20
A method of TCE degradation comprising: adding TCE water solution with concentration of 7mLTCE of 30mg/L into a 20mL headspace bottle, and introducing ultrapure N 2 To drive off oxygen, while adding pyrite (FeS) prepared in example 8 2 ) And 0.7mL of the DM cell suspension of example 1 to obtain pyrite (FeS) 2 ) The concentration in the TCE aqueous solution was 0.5g/L, the OD of the cells at 600nm was 0.15, adjusted to ph=8.0, and the headspace was sealed with a lid containing a polytetrafluoroethylene gasket, ensuring that the experiment was performed in anaerobic conditions. Will headspaceThe flask was placed in an anaerobic incubator and allowed to stand in the dark for anaerobic reaction for 48 hours at 30 ℃. After the experiment is finished, the headspace bottle is taken out of the anaerobic box, the concentration of TCE in the supernatant is analyzed, and the degradation rate of TCE is calculated.
Example 21
A TCE degradation process was essentially the same as example 20, with the only difference being that: pyrite (FeS) obtained in example 8 2 ) "replacement" example 9 the resulting biochar aerogel (CA) ".
Example 22
A TCE degradation process was essentially the same as example 20, with the only difference being that: pyrite (FeS) obtained in example 8 2 ) "replace" the biochar aerogel supported pyrite composite prepared in example 13.
The characterization of the surface functional groups after the reaction of the biochar aerogel supported pyrite composite in example 22 is shown in fig. 4.
As shown in fig. 7, TCE can be degraded by DM cell suspension of example 1, or can be directly degraded by the addition of an adsorbent. Whether the adsorbent is pyrite, biochar aerogel or biochar aerogel loaded pyrite composite material, the DM cell suspension and the adsorbent are added simultaneously to improve the TCE removal rate, which indicates that the material and microorganism cooperate to realize the efficient degradation of TCE. Wherein, the removal rate of TCE is maximum up to 76.5% when the biochar aerogel loaded pyrite composite material and DM cell suspension are added together (example 22). This is probably due to the strong TCE degrading ability of the biochar aerogel-loaded pyrite composite itself, and the addition of the biochar aerogel-loaded pyrite composite can regulate the colony structure of microorganisms in DM cell suspension.
The microbial community structure in the reaction system after the combined action of the biochar aerogel-supported pyrite composite material and the DM cell suspension in example 22 is tested, the proportion of each flora is shown as a column T1 in figure 1 by number, and as can be seen from figure 1, compared with the original DM cell suspension (namely T0), after the synergistic action of the biochar aerogel-supported pyrite composite material for degrading TCE, the microbial community structure in the reaction system is greatly changed, particularly the proportion of pseudomonas is increased from 19% to 62%, and the pseudomonas has been proved to have the capability of degrading TCE; second, 10.5% of the genus delford is newly present in the flora, which also has demonstrated the ability to degrade TCE. In conclusion, the biochar aerogel loaded pyrite composite material has the function of regulating and controlling the flora structure in DM cell suspension, and the proportion of bacteria with the capability of degrading TCE is obviously improved. This also explains the phenomenon that the synergistic effect of the two increases the TCE degradation ability.
Further, the effect of the order of addition of the adsorbent and DM cell suspension on TCE degradation rate was investigated.
Example 23
A method of TCE degradation comprising: adding TCE water solution with concentration of 7mLTCE of 30mg/L into a 20mL headspace bottle, and introducing ultrapure N 2 To drive off oxygen, 0.7mL of the DM cell suspension of example 1 was added to give a cell OD at 600nm of 0.15, the pH=8.0 was adjusted, the reaction was allowed to stand in the dark for 24h, and pyrite (FeS) prepared in example 8 was added 2 ) To make pyrite (FeS) 2 ) The concentration in the TCE aqueous solution was 0.5g/L, and the reaction was allowed to stand in the dark for anaerobic reaction for 24 hours. The concentration of TCE in the supernatant was analyzed and the degradation rate of TCE was calculated.
Example 24
A TCE degradation process substantially the same as example 23, the only difference being that: pyrite (FeS) obtained in example 8 2 ) "replacement" example 9 the resulting biochar aerogel (CA) ".
Example 25
A TCE degradation process substantially the same as example 23, the only difference being that: pyrite (FeS) obtained in example 8 2 ) "replace" the biochar aerogel supported pyrite composite prepared in example 13.
Example 26
A method of TCE degradation comprising: adding TCE water solution with concentration of 7mLTCE of 30mg/L into a 20mL headspace bottle, and introducing ultrapure N 2 To drive away oxygenThe pyrite (FeS) obtained in example 8 was added 2 ) To make pyrite (FeS) 2 ) The concentration in the TCE aqueous solution was 0.5g/L, and the reaction was allowed to stand in the dark for 24 hours (reaction temperature: 30 ℃ C.), and 0.7mL of the DM cell suspension of example 7 was further added so that the OD of the cells at 600nm was 0.15, and the pH was adjusted to=8.0, and the reaction was allowed to stand in the dark for 24 hours. The concentration of TCE in the supernatant was analyzed and the degradation rate of TCE was calculated.
Example 27
A TCE degradation process substantially the same as example 26, the only difference being that: pyrite (FeS) obtained in example 8 2 ) "replacement" example 9 the resulting biochar aerogel (CA) ".
Example 28
A TCE degradation process substantially the same as example 26, the only difference being that: pyrite (FeS) obtained in example 8 2 ) "replace" the biochar aerogel supported pyrite composite prepared in example 13.
At the end of the experiment, in addition to determining the concentration of TCE in the product to calculate TCE removal (fig. 8), the concentrations of intermediates in the reaction systems of example 22, example 28 and example 25, including cis 1, 2-dichloroethylene, vinyl chloride, acetylene, ethylene and ethane, were further tested as shown in table 1. If cis-1, 2-dichloroethylene and vinyl chloride were not detected in the product, it was considered that complete degradation of TCE was achieved (note in Table 1 that the addition of intermediate concentrations was not exactly equal to the concentration of TCE removed, since the main test reaction system was now solution and gas phase TCE and intermediate, with some TCE and intermediate adsorbed on the material surface. From the point of pollution remediation, the concentration of contaminants in the liquid and gas phases of the system was the main judgment).
TABLE 1 influence of the order of addition of DM cell suspensions and adsorbents on TCE degradation products
As shown in FIG. 8, although DM cell suspension was in CA or FeS 2 -Fe 0 Good growth in the presence of @ CA. However, when the adsorbent and DM cell suspension are added simultaneously to an aqueous TCE solution, the high toxicity of TCE to DM cell suspension may reduce the microbial dechlorination capacity of DM cell suspension, so the removal rate of TCE by simultaneous addition is only 76.5% at maximum, and complete degradation of TCE cannot be achieved (as shown by the product concentration in table 1).
The results of examples 26-28 demonstrate that the highest TCE removal rate of 86.7% can be achieved by adding the adsorbent for 24h and then adding the DM cell suspension for 24h, demonstrating that the adsorbent degrades high concentration TCE first, thereby reducing the high toxicity of TCE to the DM cell suspension, and that efficient TCE removal can be achieved by adding the DM cell suspension, and complete TCE degradation is facilitated (as shown by the product concentration in Table 1).
In contrast, the group of adding DM cell suspension and then adsorbent (examples 23-25) had the lowest TCE removal rate (66.1% maximum), which further demonstrates that high concentrations of TCE were toxic to DM cell suspension, resulting in reduced TCE degradation and no synergistic effect was achieved by adding the adsorbent after 24 hours.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the biochar aerogel loaded pyrite composite material is characterized by comprising the following steps of:
step 1, mixing pyrite, biochar aerogel, zero-valent iron and water, and performing ultrasonic treatment until the mixture is uniformly dispersed to obtain a first solution, wherein the ratio of pyrite to biochar aerogel to zero-valent iron is (0.5-1.5) in parts by weight: (0.5-2): (0-1);
step 2, mixing vitamin C and the first solution, standing at 60-65 ℃ for reaction for 12-12.5 h, washing and drying to obtain the biochar aerogel supported pyrite composite material, wherein the ratio of the vitamin C to the biochar aerogel is (2.5-5) in parts by weight: (0.5-1).
2. The method for preparing the biochar aerogel according to claim 1, wherein the method for preparing the biochar aerogel specifically comprises the following steps: KOH, NH 4 Cl、Na 2 S·9H 2 Mixing O and water, stirring to be uniform to obtain a solution A, mixing rhamnolipid and the solution A, stirring and reacting for 2-2.5 hours at 0-5 ℃, drying to obtain a biochar aerogel precursor, carbonizing the biochar aerogel precursor for 2-2.5 hours at 800-805 ℃ under nitrogen atmosphere, and cleaning to be neutral to obtain the biochar aerogel, wherein the KOH and NH are calculated according to parts by weight 4 Cl and Na 2 S·9H 2 The ratio of O is (1-2): (2-4): (1-2), wherein the ratio of KOH to rhamnolipid is (6.25-12.5) in parts by weight: (5-10).
3. The biochar aerogel supported pyrite composite material obtained by the preparation method according to claim 1 or 2.
4. The use of the biochar aerogel loaded pyrite composite according to claim 3 in conjunction with microorganisms for degrading trichloroethylene.
5. The application of claim 4, wherein the method for degrading trichloroethylene by the biochar aerogel loaded pyrite composite material and the microorganism is as follows: adding the biochar aerogel loaded pyrite composite material and DM cell suspension into a solution to be degraded containing TCE for degradation, wherein the DM cell suspension is a microorganism suspension, the DM cell suspension is added so that the OD value of cells at 600nm in the solution to be degraded is 0.1-0.5, and the DM cell suspension comprises the following microorganisms in number: 10 to 20 percent of pseudomonas, 30 to 40 percent of clostridium, 20 to 40 percent of pseudomonas and 5 to 20 percent of comamonas.
6. The use according to claim 4 or 5, wherein the biochar aerogel-loaded pyrite composite is added to the liquid to be degraded, allowed to stand for at least 24 hours, then the DM cell suspension is added, and the degradation is performed under anaerobic, dark conditions.
7. The use according to claim 5, wherein the method of obtaining a DM cell suspension comprises: soaking soil polluted by chlorinated hydrocarbon in normal saline for at least 12 hours, and carrying out domestication in a culture medium with gradually increased TCE concentration to obtain microbial flora, carrying out suspension treatment on the microbial flora by using the culture medium, centrifuging in a logarithmic growth phase, discarding supernatant, washing by using sterilized normal saline, and storing in the sterilized normal saline to obtain DM cell suspension, wherein the domestication comprises the following steps of repeatedly: taking supernatant into a culture medium containing TCE, and culturing for 3-10 days in an anaerobic environment.
8. The use according to claim 5, wherein the temperature of the biochar aerogel loaded pyrite composite material and the temperature of the micro-organisms for the synergistic degradation of trichloroethylene is 25-30 ℃.
9. The use according to claim 5, wherein the concentration of the biochar aerogel supported pyrite composite in the liquid to be degraded after adding the biochar aerogel supported pyrite composite is 0.01-1.0 g/L.
10. The use according to claim 7, characterized in that the acclimation uses a medium with a TCE concentration of 10-50 mg/L.
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