CN113943580A - Soil remediation material with dual functions of adsorption and degradation, and preparation and application thereof - Google Patents
Soil remediation material with dual functions of adsorption and degradation, and preparation and application thereof Download PDFInfo
- Publication number
- CN113943580A CN113943580A CN202010685502.8A CN202010685502A CN113943580A CN 113943580 A CN113943580 A CN 113943580A CN 202010685502 A CN202010685502 A CN 202010685502A CN 113943580 A CN113943580 A CN 113943580A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- vinasse
- based porous
- modified
- soil remediation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002689 soil Substances 0.000 title claims abstract description 85
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 72
- 230000015556 catabolic process Effects 0.000 title claims abstract description 68
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 68
- 238000005067 remediation Methods 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000006870 function Effects 0.000 title claims description 32
- 230000009977 dual effect Effects 0.000 title claims description 26
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 105
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 98
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 70
- 244000005700 microbiome Species 0.000 claims abstract description 40
- 230000000593 degrading effect Effects 0.000 claims abstract description 18
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 230000003213 activating effect Effects 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 230000000813 microbial effect Effects 0.000 claims description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 239000000661 sodium alginate Substances 0.000 claims description 15
- 235000010413 sodium alginate Nutrition 0.000 claims description 15
- 229940005550 sodium alginate Drugs 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 239000012190 activator Substances 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000012258 culturing Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 230000002308 calcification Effects 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000008055 phosphate buffer solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 21
- 238000011282 treatment Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 256
- 238000006065 biodegradation reaction Methods 0.000 description 38
- 230000000694 effects Effects 0.000 description 29
- 230000004913 activation Effects 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 14
- 241000589516 Pseudomonas Species 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000002028 Biomass Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000004134 energy conservation Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 238000011081 inoculation Methods 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000001963 growth medium Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 5
- -1 hydroxide ions Chemical class 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003900 soil pollution Methods 0.000 description 4
- 208000004434 Calcinosis Diseases 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 241000589291 Acinetobacter Species 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- 241000186146 Brevibacterium Species 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 241001504070 Huperzia Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 241000186547 Sporosarcina Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002829 nitrogen Chemical class 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000011514 vinification Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
- A01B79/02—Methods for working soil combined with other agricultural processing, e.g. fertilising, planting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
- C12N11/082—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C12N11/084—Polymers containing vinyl alcohol units
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Genetics & Genomics (AREA)
- Wood Science & Technology (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- General Health & Medical Sciences (AREA)
- Soil Sciences (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Environmental Sciences (AREA)
- Mechanical Engineering (AREA)
- Mycology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses an adsorption and degradation bifunctional soil remediation material and preparation and application thereof. The modified vinasse-based porous carbon is a material which is prepared by using vinasse as a raw material and modifying the vinasse by adopting potassium hydroxide and has the performance of adsorbing polycyclic aromatic hydrocarbon. The immobilized microorganism adsorbing material is a dual-function type vinasse adsorbing material of 'adsorbing and degrading', and the technical purpose of adsorbing and degrading PAHs is synchronously realized; the method is used for soil remediation, can realize the recycling of waste vinasse, treat waste with waste, reduce the pressure of the waste to the environment and achieve the aim of saving energy on the one hand, can directly degrade PAHs on the other hand, does not need secondary treatment, directly eliminates harm, achieves the aim of reducing emission and accords with the environmental protection concepts of treating waste with waste and saving energy and reducing emission.
Description
Technical Field
The invention belongs to the technical field of environmental pollution treatment, relates to application of a modified vinasse adsorbent and a microorganism immobilization technology, and particularly relates to a soil remediation material with dual functions of adsorption and degradation. The invention also provides a preparation method and application of the material.
Background
Soil is an important environmental medium upon which humans and other organisms are based for survival and proliferation. With the development of industry and agriculture and the acceleration of industrialization, various pollutants are generated in large quantity and are finally discharged into the environment, so that serious environmental pollution is caused. In addition to heavy metals, Persistent Organic Pollutants (POPs) are a class of pollutants that are ubiquitous in the soil environment. Persistent organic pollutants have attracted widespread attention from governments, academic circles and their public communities due to serious harm to human health and the global ecological environment.
Polycyclic Aromatic Hydrocarbons (PAHs) are one of the focuses of persistent organic pollutants. Polycyclic Aromatic Hydrocarbons (PAHs) have been widely regarded by various countries for many years as pollutants widely present in the environment, have extremely strong carcinogenic, teratogenic and mutagenic effects, and also have neurotoxicity. The toxicity of PAHs has a certain correlation with the molecular weight, low-ring aromatic hydrocarbon has obvious toxic and side effects on aquatic organic organisms such as fish, algae and the like, and high-ring aromatic hydrocarbon does not have the effect but shows three-cause effect. The soil PAHs pollution has the characteristics of long-term property, concealment, irreversibility, easy adsorption on solid particles, easy migration, high local concentration, difficult complete decomposition or disappearance and the like. PAHs in the soil can be repaired to realize in-situ PAHs degradation, harm is directly eliminated, the land available area is enlarged, and the purposes of energy conservation and emission reduction are achieved.
PAHs contamination remediation techniques generally include physical remediation, chemical remediation, and biological remediation. The traditional physical remediation mainly adopts the means of soil removal or isolation by means of soil burning, landfill, thermal desorption, steam leaching, solidification and the like to achieve the purpose of remediation. Compared with physical repair, the chemical repair technology is developed earlier and is widely used. The main chemical repair technologies include a chemical oxidation method, a chemical leaching method, a supercritical extraction technology, a subcritical extraction technology and a photocatalytic degradation technology. Although the physical repair and the chemical repair are developed earlier, the defects exist to a certain extent, such as poor operability, limited removal effect, high cost, secondary pollution to the environment and the like. The microbial degradation is a pollution remediation technology which can convert organic matters with high toxicity and complex structure into compounds with low toxicity or no toxicity and simple structure, has the advantages of high efficiency, low cost, less pollution and the like, meets the requirements of energy conservation and emission reduction, and is the most popular soil remediation technology in recent years.
The biomass charcoal is a product of high-temperature pyrolysis of biomass under an anoxic condition, and is a carbon-rich solid substance. The raw materials for preparing the biomass charcoal are wide in source, and sludge, industrial organic wastes, agricultural wastes and the like can be used as the raw materials. The biomass charcoal has large surface area and high micropores, has strong adsorption capacity, and can strongly adsorb various organic pollutants such as PAHs (polycyclic aromatic hydrocarbons) and the like; meanwhile, the carbon and nitrogen fixing agent has a good fixing effect on carbon and nitrogen, and can reduce the emission of greenhouse gases and slow down global warming when being applied to soil. In addition, the application of the biomass charcoal has important practical significance for resource utilization of waste biomass. The vinasse is one of the excellent raw materials for preparing the biomass charcoal.
The wine making industry in China can generate a large amount of vinasse every year, and the comprehensive utilization rate of the vinasse is not high. At present, most of vinasse is directly and primarily utilized, such as for culturing edible fungi, preparing feed, producing methane and the like, the utilization level and the utilization rate are low, and the added value is low. The primary utilization of the vinasse prevents the residual rich cellulose, hemicellulose, lignin and other components in the vinasse from being reasonably and effectively utilized, and the vinasse is acidic and is easy to decay and deteriorate, so that pungent odor, harmful microorganisms and the like are generated. Therefore, if the waste lees are not properly utilized or disposed of, not only is resources wasted, but also the surrounding environment is seriously threatened.
In recent years, the application of immobilized microbial technology in bioremediation is becoming a research hotspot. Immobilized microbial technology is a modern biotechnology that chemically or physically confines or localizes free microbes in a certain spatial range, retains its inherent activity, and can be used repeatedly and continuously. The technology can provide a favorable barrier for microorganisms, protect the microorganisms from predation of protozoa and the influence of severe environment, reduce competition with indigenous bacteria, and improve the soil environment to facilitate material transmission, thereby improving the survival rate of immobilized bacteria in soil and the degradation rate of the immobilized bacteria to pollutants.
Disclosure of Invention
Aiming at the defects of the prior art, the method takes waste vinasse as a raw material, and carries out pretreatment, high-temperature carbonization and chemical modification on the vinasse aiming at different properties of polycyclic aromatic hydrocarbon pollutants in soil to prepare the vinasse adsorbing material, namely the modified vinasse-based porous carbon. The microbial thallus capable of effectively degrading the polycyclic aromatic hydrocarbon is fixed on the modified vinasse-based porous carbon through an adsorption and embedding immobilization technology to prepare the adsorption and degradation dual-function soil remediation material which is used for treating the polycyclic aromatic hydrocarbon in soil, does not need secondary treatment, directly degrades and eliminates harm, opens up a new path for efficient resource utilization of waste vinasse, and solves the pollution problem of the polycyclic aromatic hydrocarbon in the soil, thereby realizing the environment-friendly concept of treating waste with waste and the purposes of energy conservation and emission reduction.
In order to achieve the above object, the present invention adopts the following technical solutions.
The soil remediation material with the dual functions of adsorption and degradation comprises modified vinasse-based porous carbon, wherein microorganisms for degrading polycyclic aromatic hydrocarbons are embedded and carried by the modified vinasse-based porous carbon.
The main component of the vinasse is cellulose, and the vinasse can be used as a raw material for preparing a vinasse biomass adsorbent after high-temperature pyrolysis and chemical modification under the anaerobic condition. The modified vinasse-based porous carbon is a material with the performance of adsorbing polycyclic aromatic hydrocarbon, which is prepared by taking vinasse as a raw material, adopting strong alkaline substances for high-temperature activation and modifying by a nitrogen source solution. The invention explains the preparation method of the modified vinasse-based porous carbon, and concretely comprises the steps of mixing vinasse with an activating agent, drying, activating for 1-4 hours at 500-800 ℃ by taking nitrogen as a protective gas, and obtaining activated porous carbon; and (3) placing the activated porous carbon in a nitrogen source solution for soaking, filtering and washing to be neutral, and drying to obtain the modified vinasse-based porous carbon.
As a preferred embodiment of the modified vinasse-based porous carbon, a strong alkaline substance is selected as the activating agent. The strong alkaline substance refers to a substance of which all anions ionized in an aqueous solution are hydroxide ions and is divided into organic strong base and inorganic strong base. The organic strong base is selected from organic metal compounds, such as organic metal lithium compound, Grignard reagent, alkyl copper lithium, etc., or selected from sodium alkoxide, potassium alkoxide, or selected from guanidine, quaternary ammonium base, etc. The inorganic strong base is selected from amino compound, partial silicide, alkali metal hydride, alkali metal hydroxide, alkaline earth metal hydroxide, etc. As one of the preferred embodiments of the present invention, the activating agent is potassium hydroxide (KOH) among alkali metal hydroxides. Based on the technical teaching of the present invention, those skilled in the art will have an incentive to replace potassium hydroxide with sodium hydroxide (NaOH) with similar physicochemical properties, or other strong alkaline compounds with the same alkalinity as potassium hydroxide, or stronger alkalinity than potassium hydroxide, or mixtures of two or more specific compounds in the strong alkaline substances, so as to realize the preparation of the modified distillers' grain-based porous carbon.
As a preferred embodiment of the modified vinasse-based porous carbon, nitrogen is used as protective gas, and the purpose of the nitrogen is to create an oxygen-free condition for high-temperature activation treatment of vinasse. Based on the teachings of the present invention, one of ordinary skill in the art will be motivated to select other inert gases as the shielding gas for the high temperature activation of the distiller's grains.
In a preferred embodiment of the modified porous carbon based on distillers' grains according to the present invention, the nitrogen source is one of dicyandiamide, melamine, ammonium chloride, and urea. Based on the teachings of the present invention, one of ordinary skill in the art would be motivated to select other nitrogen (N) -containing compounds as the nitrogen source for preparing the modified distillers' grain-based porous carbon. The nitrogen source solution and the preparation thereof may be an aqueous solution of one of dicyandiamide, melamine, ammonium chloride and urea, an aqueous solution of two or more of dicyandiamide, melamine, ammonium chloride and urea may be used, or a mixed solution of one or more of dicyandiamide, melamine, ammonium chloride and urea aqueous solution may be used.
Based on the above specific embodiment, the invention further provides a preferable preparation method of the modified distiller's grain-based porous carbon, which comprises the following steps: ultrasonically mixing the vinasse and an activating agent for 0.5-2h, drying in a drying oven at 120 ℃ for 8-12h, and activating at 500-800 ℃ for 1-4 h by taking nitrogen as protective gas to obtain activated porous carbon; placing the activated porous carbon in a nitrogen source solution at 30-90 ℃ for soaking for 3-5 h, filtering and washing to be neutral, and drying at 100 ℃ to obtain the modified vinasse-based porous carbon;
the activating agent is potassium hydroxide, and the mixing mass ratio of the potassium hydroxide to the vinasse is 1: 1-3: 1;
the nitrogen source solution is one or more of aqueous solution of dicyandiamide, melamine, ammonium chloride and urea.
Therefore, the modified vinasse-based porous carbon is prepared from vinasse serving as a raw material, can selectively adsorb polycyclic aromatic hydrocarbons in soil, can realize recycling of the vinasse in solid state fermentation to achieve the purpose of energy conservation, and can also be used for repairing the soil containing the polycyclic aromatic hydrocarbons. The modified vinasse-based porous carbon is combined with a microbial immobilization technology to prepare the soil remediation material with the dual functions of adsorption and degradation, and the soil remediation material can be directly used for degrading polycyclic aromatic hydrocarbons in soil and has dual effects of adsorption and degradation of polycyclic aromatic hydrocarbons, so that the purpose of remediation of polluted soil is achieved, and the environment-friendly concept of energy conservation and emission reduction is realized.
The technical scheme of the invention is further elaborated, the polycyclic aromatic hydrocarbon has long residual time in soil, is difficult to naturally degrade, has toxic and side effects on the environment closely related to the molecular weight, has obvious toxic and side effects on aquatic organic organisms such as fish, algae and the like, and has three causing effects on polycyclic aromatic hydrocarbon with high molecular weight. The technical scheme of the invention aims to realize the direct degradation of the low-molecular-weight polycyclic aromatic hydrocarbon with 2-3 benzene rings in soil. As will be readily understood by those of ordinary skill in the art, low molecular weight polycyclic aromatic hydrocarbons are organic compounds such as naphthalene, acenaphthylene, fluorene, phenanthrene, and the like.
The technical scheme of the invention is further explained, and the limitation of the microorganism is that the polycyclic aromatic hydrocarbon can be directly degraded under the natural environment condition of soil, and the microorganism can be combined with the modified vinasse-based porous carbon and has the biological property of directly degrading the polycyclic aromatic hydrocarbon. The microorganism is preferably selected from the strains of genus Ronobacterium, Huperzia, Sporosarcina, Pseudomonas, Brevibacterium, and Acinetobacter which can degrade the polycyclic aromatic hydrocarbon. Regarding the combination mode of the microorganism and the modified vinasse-based porous carbon, the microorganism can be attached to the surface of the modified vinasse-based porous carbon, or placed in the physical space of the modified vinasse-based porous carbon in a specific mode, or the microorganism and the modified vinasse-based porous carbon exist in the two modes. Based on the combination mode, the microorganism degrades the polycyclic aromatic hydrocarbon on the surface of the modified vinasse-based porous carbon and/or in the modified vinasse-based porous carbon.
Furthermore, the invention also provides a preparation method of the soil remediation material with dual functions of adsorption and degradation, which comprises the following steps,
mixing the microorganism suspension subjected to enrichment culture with the modified distiller's grain-based porous carbon to obtain microorganism immobilized modified distiller's grain-based porous carbon;
adding the microorganism immobilized modified vinasse-based porous carbon into a mixed colloid of sodium alginate and polyvinyl alcohol to form a prefabricated body;
and calcification of the prefabricated body to obtain the soil remediation material with the adsorption and degradation functions.
As a preferable embodiment of the preparation method of the adsorption and degradation dual-function soil remediation material, the preparation method comprises the following steps,
culturing the microorganism under proper conditions, enriching and concentrating, and preparing the microorganism suspension by using a phosphate buffer solution;
mixing the microbial suspension with the modified vinasse-based porous carbon, and oscillating at constant temperature to obtain the microbial immobilized modified vinasse-based porous carbon;
mixing sodium alginate and polyvinyl alcohol, heating and stirring to obtain a mixed colloid;
adding the microorganism immobilized modified vinasse-based porous carbon into the mixed colloid to form a prefabricated body;
and (3) placing the prefabricated body into calcium chloride, calcifying, washing with sterilized deionized water to obtain the soil remediation material with the dual functions of adsorption and degradation, and storing for later use.
In addition, the invention further provides the application of the soil remediation material with the dual functions of adsorption and degradation in soil remediation.
As a further optimization of the soil remediation application, the soil remediation material with the dual functions of adsorption and degradation is used for adsorbing and degrading polycyclic aromatic hydrocarbons in soil, and particularly directly degrades low-molecular-weight polycyclic aromatic hydrocarbons with 2-3 benzene rings in soil.
Compared with the prior art, the soil remediation material with double functions of adsorption and degradation, and the preparation method and the application thereof have at least the following beneficial effects or advantages.
The soil remediation material with the dual functions of adsorption and degradation comprises modified vinasse-based porous carbon, wherein microbial strains capable of degrading polycyclic aromatic hydrocarbons are embedded and carried by the modified vinasse-based porous carbon. The modified vinasse-based porous carbon is prepared by using vinasse as a raw material, strong alkaline substances such as KOH and the like as an activating agent and a nitrogen source solution as a modifying agent, and has a strong removing effect on PAHs in polluted soil. The modified vinasse-based porous carbon and the microbial strain capable of degrading polycyclic aromatic hydrocarbons are prepared into the adsorption and degradation dual-function soil remediation material by adopting an embedding immobilization technology, and the adsorption and degradation dual-function vinasse adsorption material is a 'adsorption and degradation' dual-function type vinasse adsorption material and synchronously realizes the technical purpose of adsorbing and degrading PAHs so as to remediate polluted soil.
The soil remediation material with the dual functions of adsorption and degradation is used for soil remediation, so that the waste vinasse can be recycled, the pressure of the waste vinasse on the environment is reduced, the purpose of energy conservation is achieved, the PAHs can be directly degraded, secondary treatment is not needed, harm is directly eliminated, the purpose of emission reduction is achieved, and the environment-friendly concept of waste treatment by waste and energy conservation and emission reduction is met.
Drawings
FIG. 1 shows the adsorption performance of modified vinasse-based porous carbon prepared by different activators on polycyclic aromatic hydrocarbon Phenanthrene (PHE).
FIG. 2 shows that KOH is used as an activating agent to prepare modified vinasse-based porous carbon, and the dosage of the modified vinasse-based porous carbon has the adsorption performance on polycyclic aromatic hydrocarbon Phenanthrene (PHE).
FIG. 3 shows that KOH is used as an activating agent to prepare modified vinasse-based porous carbon, and the polycyclic aromatic hydrocarbon Phenanthrene (PHE) adsorption performance is improved by different activation times.
FIG. 4 shows the adsorption performance of the modified vinasse-based porous carbon prepared by using KOH as an activating agent at different activation temperatures on polycyclic aromatic hydrocarbon Phenanthrene (PHE).
FIG. 5, effect of degradation time on biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE).
FIG. 6 shows the effect of rotational speed on the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE).
FIG. 7, effect of pH on biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE).
FIG. 8 shows the effect of inoculum size on the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE).
FIG. 9, effect of medium nitrogen source on biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE).
FIG. 10, effect of temperature on biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE).
Detailed Description
In order to facilitate understanding of the objects, technical solutions and effects of the present invention, the present invention will be further described in detail with reference to examples.
Preparation and performance characterization of modified vinasse-based porous carbon
The present example illustrates the preparation method and performance characterization of the modified distillers' grain-based porous carbon, and the preparation method is described in detail as follows.
Cleaning distiller's grains or wine Dregs (DG), drying, pulverizing the distiller's grains with particle size of 40-150 meshes, mixing with activating agent by ultrasonic for 0.5-2 hr, drying in 120 deg.C oven for 8-12 hr, and protecting with N gas at 500-800 deg.C2And activating for 1-4 h in the atmosphere to obtain the activated porous carbon.
And (3) placing the activated porous carbon in a nitrogen source solution at the temperature of 30-90 ℃ for soaking for 3-5 h, filtering and washing to be neutral, and drying at the temperature of 100 ℃ to obtain the modified vinasse-based porous carbon.
The activating agent is potassium hydroxide, and the mixing mass ratio of the potassium hydroxide to the vinasse is 1: 1-3: 1.
In this embodiment, the source of the distiller's grains (dregs) is not particularly limited, and may be distiller's grains produced by brewing white spirit with the largest proportion, or other types of distiller's grains. The drying temperature of the distiller's grains is not particularly limited in this embodiment, and may be set to any temperature that can dry the distiller's grains. The grain size of the crushed lees is not particularly limited in this embodiment, but it is generally preferable that the grain size of the crushed lees is 40 to 150 mesh.
In the embodiment, polycyclic aromatic hydrocarbon Phenanthrene (PHE) is selected as a processing object to characterize the adsorption performance of the modified vinasse-based porous carbon. Setting the dosage of the modified vinasse-based porous carbon to be 6.5 g.L-1Initial concentration of polycyclic aromatic Hydrocarbon Phenanthrene (PHE) 200 mg.L-1The adsorption performance of the polycyclic aromatic hydrocarbon Phenanthrene (PHE) by factors such as the type of the activator, the using amount of the activator, the activation time, the activation temperature and the like is considered, and the results are shown in figures 1 to 4.
Regarding the selection of the activator class, phosphoric acid is a common vinasse modifier in the prior art, and the adsorption performance of the modified vinasse-based porous carbon prepared by different activators (KOH and phosphoric acid) on polycyclic aromatic hydrocarbon Phenanthrene (PHE) is shown in figure 1. The blank in figure 1 is a modified distillers' grain-based porous carbon prepared without activator, represented as Origin in figure 1. As can be seen from fig. 1, the adsorption rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE) by the modified distiller's grain-based porous carbon prepared by using KOH as an activator is 89.42%, and the adsorption rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE) by the modified distiller's grain-based porous carbon prepared by using phosphoric acid as an activator is 66.9%, so that the adsorption rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE) by the modified distiller's grain-based porous carbon can be significantly improved by using KOH as an activator, and the adsorption effect of Phenanthrene (PHE) is significantly better than that of phosphoric acid.
FIG. 2 shows the adsorption performance of KOH as an activator for preparing modified vinasse-based porous carbon, wherein the dosage of the modified vinasse-based porous carbon is used for polycyclic aromatic hydrocarbon Phenanthrene (PHE). Setting the mixing mass ratio of potassium hydroxide to vinasse to be 1: 1-3: 1, wherein the adsorption rate of the prepared modified vinasse-based porous carbon to polycyclic aromatic hydrocarbon Phenanthrene (PHE) is over 85%; when the mass ratio of KOH to Distilled Grains (DG) is 1.5:1, the adsorption rate is the maximum and reaches 89.6 percent; when the mass ratio of KOH to Distilled Grains (DG) is more than 1.5:1, the adsorption rate is reduced.
FIG. 3 shows the adsorption performance of the modified distiller's grain-based porous carbon prepared by using KOH as an activating agent on polycyclic aromatic hydrocarbon Phenanthrene (PHE) with different activation times. The activation time is set to be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h and 4h in sequence, as shown in figure 3, the activation time is within the range of 1-4 h, the prepared modified vinasse-based porous carbon has good adsorption rate to Phenanthrene (PHE), and the measured adsorption rate is over 86%; the activation is carried out for 2 hours, the highest phenanthrene adsorption rate is achieved, and the maximum phenanthrene adsorption rate reaches 88.4%.
Regarding the determination of the activation temperature, the adsorption performance of the modified vinasse-based porous carbon prepared by using KOH as an activating agent at different activation temperatures (500-800 ℃) on polycyclic aromatic hydrocarbon Phenanthrene (PHE) is shown in FIG. 4. As can be seen from FIG. 4, in a given temperature range, the adsorption rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE) by the modified vinasse-based porous carbon is above 86%, the activation temperature is 600 ℃, and the adsorption rate reaches a maximum of 89.6%.
Regarding the selection of the kind of modified nitrogen source required for preparing the modified distillers' grain-based porous carbon, the nitrogen source solution according to this embodiment is an aqueous solution of one or more of dicyandiamide, melamine, ammonium chloride, and urea, and more preferably an aqueous urea solution.
When the nitrogen source solution is used specifically, a nitrogen source solution with the mass fraction of 0.01-0.5% is prepared. In light of the teachings of this example, one of ordinary skill in the art can select other types of modified nitrogen sources to achieve the preparation of the modified distillers' grain-based porous carbon of this example. Regarding optimization of modification parameter conditions, the hydrothermal modification temperature is preferably 30-90 ℃, and the soaking time is preferably 3-5 h.
In conclusion, the modified vinasse-based porous carbon prepared by the method has a good adsorption effect on polycyclic aromatic hydrocarbon Phenanthrene (PHE).
Biodegradation of Phenanthrene (PHE) by microbial strains
As described above, the microorganism of the present invention is preferably selected from the genera of genus Ronobacterium, Huperzia, Sporosarcina, Pseudomonas, Brevibacterium and Acinetobacter which are capable of degrading polycyclic aromatic hydrocarbons. In this example, pseudomonas strains capable of degrading polycyclic aromatic hydrocarbon phenanthrene are selected as test bacteria, and the influence of the microbial strains on polycyclic aromatic hydrocarbon Phenanthrene (PHE) degradation efficiency under different factor conditions is discussed.
The single-factor variables examined in this example include degradation time, rotation speed, pH, inoculation amount, medium nitrogen source, temperature, and other variables are controlled to be the same, 10mL of pseudomonas strain suspension is transferred to a 250mL triangular flask containing 100mL of inorganic salt liquid medium, each group of medium is inoculated to 3 culture dishes, cyclohexane is added to degradation liquid after 7 days of culture, extraction is repeated for 2 times by a separating funnel, and the supernatant is taken to measure the absorbance at the wavelength of 293nm, and the degradation rate is calculated. The test results are shown in fig. 5 to 10.
FIG. 5 shows the effect of degradation time on the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE). As can be shown in FIG. 5, the degradation rate after 3d of action reaches 25.20%, the degradation rate after 5d of action is 34.43%, and the degradation rate after 7d of action is 45.60%, the biodegradation rate of the strain on the polycyclic aromatic hydrocarbon Phenanthrene (PHE) is continuously increased along with the extension of the degradation time within 7 days, the degradation of the strain on the phenanthrene is not inhibited, and the biological performance of rapidly degrading the polycyclic aromatic hydrocarbon Phenanthrene (PHE) is shown.
FIG. 6 shows the effect of rotational speed on the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE). When the rotating speed is set to be 120rmp, the biodegradation rate of the bacterial strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) within 7d is 52.70 percent; when the rotating speed is set to be 160rmp, the biodegradation rate of the bacterial strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) within 7d is 48.30 percent; when the rotation speed is set to be 200rmp, the biodegradation rate of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) in 7d is 46.03%. Therefore, with the increase of the culture rotating speed, the biodegradation efficiency of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) is continuously reduced within 7d, the side surface shows the requirement of the strain on oxygen during aerobic degradation of phenanthrene, and the biodegradation rate of the strain adopting screening in a plateau area is lower than that of an oxygen-rich area.
FIG. 7 shows the effect of pH on the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE). When the pH value of the culture medium is 6, the biodegradation rate of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) in 7d reaches 54.50 percent; when the pH value of the culture medium is 7, the biodegradation rate of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) in 7d reaches 54.25 percent; when the pH value of the culture medium is 8, the biodegradation rate of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) within 7d reaches 55.20%, and the strain has no obvious difference between treatments, but has the trend that the biodegradation rate is reduced and then increased; it can be presumed that the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE) under the acidic or alkaline soil condition by using the screened strain is higher than that in neutral soil.
FIG. 8 shows the effect of inoculum size on the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE). When the inoculation amount is 5mL, the biodegradation rate of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) in 7d reaches 43.40%; when the inoculation amount is 10mL, the biodegradation rate of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) in 7d reaches 52.30%; when the inoculation amount is 15mL, the biodegradation rate of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) in 7d reaches 58.50%. Therefore, the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE) is increased along with the increase of the inoculation amount, and the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE) can be effectively improved by properly increasing the inoculation amount.
FIG. 9 shows the effect of different medium nitrogen sources on the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE). Setting the pH of the culture medium to 7, the inoculation amount to 15mL, the degradation time to 7d, the degradation temperature to 42 ℃ and the rotation speed to 120rmp, and using NaNO3Is a nitrogen source, the biodegradation rate of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) is the highest, can reach 57.33 percent, and is superior to the selected urea and (NH)4)2SO4As is the case.
FIG. 10 shows the effect of temperature on the biodegradation rate of polycyclic aromatic hydrocarbon Phenanthrene (PHE). Setting the pH value of the culture medium to be 7, the inoculation amount to be 15mL, the degradation time to be 7d and NaNO3When the strain is a nitrogen source and the rotating speed is 120rmp and the degradation temperature is set to be 40 ℃, the biodegradation rate of the strain on polycyclic aromatic hydrocarbon Phenanthrene (PHE) is the highest and can reach 63.1 percent; when the degradation temperature is set to be 34 ℃, the biodegradation rate of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) is 61.47 percent; when the degradation temperature is set to 37 ℃, the biodegradation rate of the strain to polycyclic aromatic hydrocarbon Phenanthrene (PHE) is 52.5 percent. Therefore, the degradation temperature can obviously influence the biodegradation rate of the strain on the polycyclic aromatic hydrocarbon Phenanthrene (PHE).
In conclusion, the pseudomonas strain screened by the embodiment has a good degradation effect on the polycyclic aromatic hydrocarbon Phenanthrene (PHE), and can realize the direct degradation of the polycyclic aromatic hydrocarbon Phenanthrene (PHE) so as to achieve the purpose of removing the polycyclic aromatic hydrocarbon.
Preparation and performance characterization of soil remediation material with dual functions of adsorption and degradation
The embodiment provides a preparation method of the soil remediation material with the dual functions of adsorption and degradation, and the technical idea is as follows: mixing the microorganism suspension subjected to enrichment culture with the modified distiller's grain-based porous carbon to obtain microorganism immobilized modified distiller's grain-based porous carbon; adding the microorganism immobilized modified vinasse-based porous carbon into a mixed colloid of sodium alginate and polyvinyl alcohol to form a prefabricated body; and calcification of the prefabricated body to obtain the soil remediation material with the adsorption and degradation functions.
As further elaboration of the technical idea, the preparation method of the adsorption and degradation bifunctional soil remediation material comprises the following steps: culturing the microorganism under proper conditions, enriching and concentrating, and preparing the microorganism suspension by using a phosphate buffer solution; mixing the microbial suspension with the modified vinasse-based porous carbon, and oscillating at constant temperature to obtain the microbial immobilized modified vinasse-based porous carbon; mixing sodium alginate and polyvinyl alcohol, heating and stirring to obtain a mixed colloid; adding the microorganism immobilized modified vinasse-based porous carbon into the mixed colloid to form a prefabricated body; and (3) placing the prefabricated body into calcium chloride, calcifying, washing with sterilized deionized water to obtain the soil remediation material with the dual functions of adsorption and degradation, and storing for later use.
Taking the pseudomonas strain as an example, the soil remediation material with double functions of adsorption and degradation is prepared. Culturing a pseudomonas strain under a proper condition, and after the strain is cultured to a logarithmic growth phase, carrying out centrifugal concentration for 15min at a rotating speed of 10000r/min to obtain pseudomonas liquid; adding 1mL of pseudomonas bacterial liquid into 50mL of sterilized liquid activation culture medium, carrying out enrichment culture in a constant-temperature shaking table for 24h, centrifuging at 5000r/min to collect thalli, preparing pseudomonas bacterial suspension by using a phosphate buffer solution, and placing the pseudomonas bacterial suspension in a refrigerator for later use; mixing the pseudomonas suspension and the modified vinasse-based porous carbon, wherein the mixing proportion of the pseudomonas suspension and the modified vinasse-based porous carbon is preferably (1-100): 1 in parts by mass, oscillating at constant temperature of 30 ℃ and 150r/min for 2 hours to obtain microorganism immobilized modified vinasse-based porous carbon, and placing the modified vinasse-based porous carbon in a refrigerator for later use; mixing Sodium Alginate (SA) and polyvinyl alcohol (PVA) according to a mass ratio of 1: 9-1: 20, heating in a water bath (about 90 ℃) and continuously stirring for dissolving, cooling to obtain a mixed colloid (about 40 ℃), and adding 15mL of the microorganism immobilized modified vinasse-based porous carbon after the colloid is cooled to form a preform; and (3) injecting the prefabricated body into calcium chloride by using a needle tube, calcifying, washing by using sterilized deionized water to prepare the soil remediation material with the dual functions of adsorption and degradation, and storing for later use.
The mixture of polyvinyl alcohol and sodium alginate has the characteristics of high strength, high permeability, good biocompatibility, strong stability and the like. The research of the embodiment shows that if the dosage of the polyvinyl alcohol is too high, the mass transfer resistance between the substrate and the product can be increased, especially the transfer of oxygen is limited, and the balling is difficult, and the balling effect and the action performance are influenced by too little and too much dosage of the sodium alginate. In this example, the best combination of polyvinyl alcohol (PVA) and Sodium Alginate (SA) was selected to be 10% PVA + 0.5% SA.
The optimal use combination of selected polyvinyl alcohol (PVA) and Sodium Alginate (SA) is used for embedding the microorganism immobilized modified vinasse-based porous carbon, the addition amount of the microorganism immobilized modified vinasse-based porous carbon is 15mL, and the soil remediation material with double functions of adsorption and degradation is obtained after calcification treatment. The pH value of the inorganic salt liquid culture medium is set to be 7, the degradation temperature is set to be 42 ℃, the rotating speed is set to be 120rmp, and the biodegradation result of the prepared adsorption and degradation bifunctional soil remediation material on polycyclic aromatic hydrocarbon Phenanthrene (PHE) is shown in table 1.
TABLE 1 biodegradation of polycyclic aromatic Hydrocarbon Phenanthrene (PHE) by adsorption and degradation bifunctional soil remediation materials
As can be seen from Table 1, the biodegradation effect of the prepared adsorption and degradation bifunctional soil remediation material on polycyclic aromatic hydrocarbon Phenanthrene (PHE) is superior to that of the prepared microbial strain on polycyclic aromatic hydrocarbon Phenanthrene (PHE), and the biodegradation rate of the prepared adsorption and degradation bifunctional soil remediation material on polycyclic aromatic hydrocarbon Phenanthrene (PHE) in 5 days reaches 94.6%, which is obviously higher than that of the microbial strain on polycyclic aromatic hydrocarbon Phenanthrene (PHE) in 7 days (70.71%).
Economic benefit analysis of adsorption and degradation dual-function soil remediation material
According to the national soil pollution condition survey bulletin issued in 2014, the national soil pollution exceeding rate reaches 16.1%, and the Chinese soil pollution threatens the sustainable utilization of land resources and the ecological safety of agricultural products. The farmlands polluted by organic pollutants in China reach 3600 million hectares, and the types of the pollutants comprise petroleum, polycyclic aromatic hydrocarbon, pesticide, organic chlorine and the like. The area of the land seriously polluted by petroleum caused by oil field exploitation reaches 1 ten thousand hectares. The existing cultivated land in China is nearly 1/5 polluted to different degrees, the polluted soil can cause the yield reduction of crops, and even the pollutant in agricultural products can exceed the standard, thereby further harming the human health.
Taking the example that Beijing construction environment restoration Limited liability company adopts thermal desorption treatment technology to restore the soil of the pesticide-left polluted site in Jiangsu province, the site pollutants are mainly benzene series, PAHs and other volatile or semi-volatile organic compounds, and the amount of the restored soil is 24.7 ten thousand meters3The engineering period is up to 440 days. The project costs 1400 ten thousand yuan in total, calculated at the basic cost of soil remediation.
The soil remediation material with the dual functions of adsorption and degradation is 18000 yuan per ton and 24.7 ten thousand meters per ton3The field of (1) can save about 253.4 ten thousand yuan. The specific calculations are shown in tables 2 to 4.
TABLE 2 cost of soil remediation
TABLE 3 cost of adsorbing and degrading bifunctional soil remediation materials (Unit: Yuan/ton)
TABLE 4 cost savings from remediation of soil with soil remediation materials with adsorption and degradation dual functions
Therefore, a series of operations of modification and microorganism immobilization are performed on the waste vinasse, so that the waste vinasse can be recycled, the purpose of treating waste with waste is achieved, and the energy-saving purpose is achieved, and on the other hand, the immobilized microorganism adsorption material is used for soil pollution remediation, so that the manpower and material resources consumed by soil in different positions can be reduced and avoided, meanwhile, the adsorbed polycyclic aromatic hydrocarbon can be directly degraded, secondary treatment on waste gas and waste liquid is not needed, the remediation process is reduced, and the purposes of energy conservation and emission reduction are achieved. The soil remediation material with double functions of adsorption and degradation is adopted for soil remediation, the preparation process of the material is simple, the cost is low, the treatment effect is good, and the material can be invested in capital for quantitative production.
The present invention has been further described with reference to the examples, but the present invention is not limited to the above-described embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The soil remediation material with the dual functions of adsorption and degradation is characterized by comprising modified vinasse-based porous carbon, wherein microorganisms for degrading polycyclic aromatic hydrocarbons are embedded and carried by the modified vinasse-based porous carbon.
2. The soil remediation material with dual functions of adsorbing and degrading according to claim 1, wherein the modified distiller's grain-based porous carbon is prepared by the following steps: mixing the vinasse and an activating agent, drying, and activating for 1-4 hours at 500-800 ℃ by taking nitrogen as protective gas to obtain activated porous carbon; and (3) placing the activated porous carbon in a nitrogen source solution for soaking, filtering and washing to be neutral, and drying to obtain the modified vinasse-based porous carbon.
3. The soil remediation material of claim 2, wherein said activator is selected from the group consisting of a strong alkaline source.
4. The soil remediation material with dual functions of adsorbing and degrading according to claim 2, wherein the nitrogen source is one of dicyandiamide, melamine, ammonium chloride and urea.
5. The soil remediation material with dual functions of adsorption and degradation as claimed in claim 1, wherein the polycyclic aromatic hydrocarbon is a low-molecular-weight polycyclic aromatic hydrocarbon with 2-3 benzene rings in the molecular structure.
6. The adsorptive and degradable dual function soil remediation material of claim 1 wherein said microorganism degrades said polycyclic aromatic hydrocarbon on and/or within said modified distillers' grain-based porous carbon.
7. The soil remediation material with dual functions of adsorbing and degrading according to claim 2, wherein the modified distiller's grain-based porous carbon is prepared by the following steps: ultrasonically mixing the vinasse and an activating agent for 0.5-2h, drying in a drying oven at 120 ℃ for 8-12h, and activating at 500-800 ℃ for 1-4 h by taking nitrogen as protective gas to obtain activated porous carbon; placing the activated porous carbon in a nitrogen source solution at 30-90 ℃ for soaking for 3-5 h, filtering and washing to be neutral, and drying at 100 ℃ to obtain the modified vinasse-based porous carbon;
the activating agent is potassium hydroxide, and the mixing mass ratio of the potassium hydroxide to the vinasse is 1: 1-3: 1;
the nitrogen source solution is one or more of aqueous solution of dicyandiamide, melamine, ammonium chloride and urea.
8. The preparation method of the soil remediation material with dual functions of adsorption and degradation as claimed in claim 1, comprises,
mixing the microorganism suspension subjected to enrichment culture with the modified distiller's grain-based porous carbon to obtain microorganism immobilized modified distiller's grain-based porous carbon;
adding the microorganism immobilized modified vinasse-based porous carbon into a mixed colloid of sodium alginate and polyvinyl alcohol to form a prefabricated body;
and calcification of the prefabricated body to obtain the soil remediation material with the adsorption and degradation functions.
9. The method of claim 8, comprising,
culturing the microorganism under proper conditions, enriching and concentrating, and preparing the microorganism suspension by using a phosphate buffer solution;
mixing the microbial suspension with the modified vinasse-based porous carbon, and oscillating at constant temperature to obtain the microbial immobilized modified vinasse-based porous carbon;
mixing sodium alginate and polyvinyl alcohol, heating and stirring to obtain a mixed colloid;
adding the microorganism immobilized modified vinasse-based porous carbon into the mixed colloid to form a prefabricated body;
and (3) placing the prefabricated body into calcium chloride, calcifying, washing with sterilized deionized water to obtain the soil remediation material with the dual functions of adsorption and degradation, and storing for later use.
10. The use of the adsorption and degradation bifunctional soil remediation material of claim 1 for soil remediation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010685502.8A CN113943580A (en) | 2020-07-16 | 2020-07-16 | Soil remediation material with dual functions of adsorption and degradation, and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010685502.8A CN113943580A (en) | 2020-07-16 | 2020-07-16 | Soil remediation material with dual functions of adsorption and degradation, and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113943580A true CN113943580A (en) | 2022-01-18 |
Family
ID=79326607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010685502.8A Pending CN113943580A (en) | 2020-07-16 | 2020-07-16 | Soil remediation material with dual functions of adsorption and degradation, and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113943580A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115121599A (en) * | 2022-06-23 | 2022-09-30 | 天津壹鸣环境污染治理有限公司 | Soil remediation system and remediation method |
| CN116064044A (en) * | 2023-03-07 | 2023-05-05 | 北京汉科财富科技有限公司 | Soil conditioner and soil conditioning method for repairing acidification hardening and heavy metal pollution |
| JP7302086B1 (en) * | 2022-12-16 | 2023-07-03 | ミヨシ油脂株式会社 | soil conditioner |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475444A (en) * | 2014-11-04 | 2015-04-01 | 上海交通大学 | Preparation, application and usage method for biocarbon-immobilized composite pollution-degrading bacterium particle |
| CN104560938A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method and application of petroleum-degrading bacteria immobilized embedded particles |
| CN109928391A (en) * | 2019-04-02 | 2019-06-25 | 四川轻化工大学 | A kind of modified distillers ' grains matrix activated carbon and preparation method thereof |
| CN110396488A (en) * | 2019-07-18 | 2019-11-01 | 中国科学院城市环境研究所 | A kind of mixed culture and application method of degrading polycyclic aromatic hydrocarbons pollutant |
-
2020
- 2020-07-16 CN CN202010685502.8A patent/CN113943580A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560938A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method and application of petroleum-degrading bacteria immobilized embedded particles |
| CN104475444A (en) * | 2014-11-04 | 2015-04-01 | 上海交通大学 | Preparation, application and usage method for biocarbon-immobilized composite pollution-degrading bacterium particle |
| CN109928391A (en) * | 2019-04-02 | 2019-06-25 | 四川轻化工大学 | A kind of modified distillers ' grains matrix activated carbon and preparation method thereof |
| CN110396488A (en) * | 2019-07-18 | 2019-11-01 | 中国科学院城市环境研究所 | A kind of mixed culture and application method of degrading polycyclic aromatic hydrocarbons pollutant |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115121599A (en) * | 2022-06-23 | 2022-09-30 | 天津壹鸣环境污染治理有限公司 | Soil remediation system and remediation method |
| JP7302086B1 (en) * | 2022-12-16 | 2023-07-03 | ミヨシ油脂株式会社 | soil conditioner |
| CN116064044A (en) * | 2023-03-07 | 2023-05-05 | 北京汉科财富科技有限公司 | Soil conditioner and soil conditioning method for repairing acidification hardening and heavy metal pollution |
| CN116064044B (en) * | 2023-03-07 | 2023-05-30 | 北京汉科财富科技有限公司 | Soil conditioner and soil conditioning method for repairing acidification hardening and heavy metal pollution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113943580A (en) | Soil remediation material with dual functions of adsorption and degradation, and preparation and application thereof | |
| Zhang et al. | Removal of chlortetracycline from water by Bacillus cereus immobilized on Chinese medicine residues biochar | |
| CN108611292B (en) | Preparation method and application of cold-resistant ammonia oxidizing bacteria immobilized biochar ball | |
| Wang et al. | Advances in research on petroleum biodegradability in soil | |
| CN104946620A (en) | Immobilized microbial inoculant for restoring petroleum-hydrocarbon-polluted alkaline-saline soil and preparation method thereof | |
| CN108130299B (en) | Microbial strain for degrading petroleum hydrocarbon and combined repairing agent | |
| CN103045579B (en) | Microbial remediation curing adsorbing bacterial preparation applicable to marine environment petroleum pollution as well as preparation method and application of same | |
| CN102443400B (en) | Ternary composite organic pollution repairing agent containing iron oxide, humus and reducing bacteria thereof, and preparation method of repairing agent | |
| CN103484447B (en) | A kind of preparation method of oil degradation zymin and application | |
| CN104694525A (en) | Immobilization method of salt-tolerant and cold-tolerant compound strain and application of immobilization method | |
| CN110499339B (en) | Method for improving methane production efficiency by anaerobic digestion | |
| CN105013815A (en) | Biological remediation method for polycyclic aromatic hydrocarbon and heavy metal compound contaminated soil | |
| CN107570113A (en) | A kind of method for preparing charcoal using antibiotic fermentation residue and application thereof | |
| CN105695443B (en) | Triton X-100 enhanced biological charcoal immobilized microorganism material and its preparation method and application | |
| Wang et al. | Bioremediation of nitrogen-and phosphorus-polluted aquaculture sediment by utilizing combined immobilized effective microorganisms and | |
| CN114540337A (en) | Preparation method and application of microorganism immobilized composite particles | |
| CN110340138A (en) | The method of biomass carbon enhancement microbiological reparation Cr (VI)-cyanide combined contamination soil | |
| CN105524889A (en) | Preparation method of enzyme preparation for polycyclic aromatic hydrocarbon contaminated soil remediation | |
| Yang et al. | A review of emerged constructed wetlands based on biochar filler: Wastewater purification and carbon sequestration/greenhouse gas reduction | |
| CN106902737A (en) | A kind of tealeaf residue biology carbon material being modified based on Nano Silver and preparation method and application | |
| CN107617639B (en) | Method for treating polychlorinated biphenyl polluted soil by using microorganisms and mineral substances in combined manner | |
| CN105586331A (en) | Method of denitrified composite microbial inoculant | |
| Ding et al. | Wheat straw biochar and its performance in treatment of phenanthrene containing water and microbial remediation of phenanthrene contaminated soil | |
| Shi et al. | Effects of biochar immobilized microorganisms on the enzyme activity and remediation of petroleum hydrocarbon in contaminated soil | |
| Liu et al. | Microbial immobilization technology for remediation of petroleum hydrocarbon contaminated soil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |