CN114212964A - Resource utilization method for river and lake dredging sediment - Google Patents
Resource utilization method for river and lake dredging sediment Download PDFInfo
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- CN114212964A CN114212964A CN202111522328.6A CN202111522328A CN114212964A CN 114212964 A CN114212964 A CN 114212964A CN 202111522328 A CN202111522328 A CN 202111522328A CN 114212964 A CN114212964 A CN 114212964A
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- sediment
- covalent bond
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- river
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Links
- 239000013049 sediment Substances 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 claims abstract description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000009264 composting Methods 0.000 claims abstract description 77
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 47
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 45
- 239000002361 compost Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
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- 239000000126 substance Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000007605 air drying Methods 0.000 claims abstract description 10
- 239000001963 growth medium Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 84
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 41
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- 239000002245 particle Substances 0.000 claims description 36
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- 238000002360 preparation method Methods 0.000 claims description 26
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- 239000002243 precursor Substances 0.000 claims description 17
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- -1 dimethyl octadecyl Chemical group 0.000 claims description 13
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000001509 sodium citrate Substances 0.000 claims description 10
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 10
- 229940038773 trisodium citrate Drugs 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 102000002322 Egg Proteins Human genes 0.000 claims description 5
- 108010000912 Egg Proteins Proteins 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
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- 210000003278 egg shell Anatomy 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 230000007226 seed germination Effects 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 3
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- 229910001385 heavy metal Inorganic materials 0.000 abstract description 79
- 230000018044 dehydration Effects 0.000 abstract description 20
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- 208000005156 Dehydration Diseases 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 238000005189 flocculation Methods 0.000 description 20
- 230000016615 flocculation Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 19
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- 238000001179 sorption measurement Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010802 sludge Substances 0.000 description 10
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 9
- 239000008394 flocculating agent Substances 0.000 description 8
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- 239000011159 matrix material Substances 0.000 description 6
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- 238000005516 engineering process Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 229920002401 polyacrylamide Polymers 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 125000005371 silicon functional group Chemical group 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 229910052804 chromium Inorganic materials 0.000 description 2
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- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 239000010871 livestock manure Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 229910052585 phosphate mineral Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
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- 244000144977 poultry Species 0.000 description 2
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- 238000007711 solidification Methods 0.000 description 2
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- 230000005653 Brownian motion process Effects 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- NIWRYIGIWAMKRI-UHFFFAOYSA-N [Pb].[Cd].[Cu] Chemical compound [Pb].[Cd].[Cu] NIWRYIGIWAMKRI-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
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- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
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- 238000005537 brownian motion Methods 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003922 charged colloid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- UBMGRWRKCJIKMQ-UHFFFAOYSA-M dodecyl-dimethyl-(3-trimethoxysilylpropyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCC[Si](OC)(OC)OC UBMGRWRKCJIKMQ-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000768 polyamine Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/148—Combined use of inorganic and organic substances, being added in the same treatment step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/80—Separation, elimination or disposal of harmful substances during the treatment
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention relates to a resource utilization method of river and lake dredging sediment, which comprises the following steps: s1, dehydration treatment: adding the prepared covalent bond type composite flocculant @ Fe into dredged sediment3O4Uniformly stirring and mixing the mixture, coagulating the mixture, naturally settling the mixture, and removing the overlying water to obtain flocculated and dewatered bottom mud; s2, composting: adding the prepared hydroxyapatite/tobermorite @ Fe into the flocculated and dewatered bottom mud3O4Composite material, aerobic compostingThe compost product meets the requirement of maturity; s3, post-processing: and (3) air-drying the composted product, carrying out magnetic separation, and preparing the remaining humic substance and other auxiliary materials into a seedling culture medium. Compared with the traditional method for directly composting the dredged sediment, the method overcomes the problems that the dredged sediment is difficult to dewater and pretreat and the product quality is difficult to reach the standard due to high heavy metal content, and the heavy metal of the compost product can meet the standard value of organic matters for greening planting such as closed forest land, expressway or afforestation in 'organic substrate for greening'.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, and relates to a resource utilization method of river and lake dredging sediment.
Background
With the modern urbanization process and the improvement of the industrial level, a large amount of domestic sewage and industrial wastewater generated by human beings are discharged into rivers and lakes, so that the water body pollution is increasingly serious. The pollutants in the water body not only seriously weaken the self-cleaning function of the natural water body to cause the basic function of the water body to be degraded or lost, but also gradually precipitate and enrich in the bottom mud with time. The polluted bottom mud can continuously release pollutants into the water body, and becomes an endogenous source of water body pollution, so the polluted bottom mud is removed by adopting an environment-friendly dredging technology, the pollution source in the river channel can be fundamentally treated, the secondary pollution of the bottom mud to the water body is thoroughly avoided, and the method is the most effective means for treating the black and odorous water body at present. The environment-friendly dredging brings a great deal of dredged sediment which has large volume, high water content and many toxic and harmful components, thereby not only occupying a great deal of land resources, but also easily causing secondary pollution to the surrounding environment and even endangering the health of human bodies.
Dredged sediment is a mixture of clay, silt, organic matters and various minerals, is formed by long-time physical, chemical and biological actions and water body transmission and is deposited at the bottom of a water body, and is structural soil mainly comprising fine horn-shaped clay substances. The bottom sludge can adsorb most pollutants in water, mainly comprises nutrient substances (nitrogen, phosphorus, potassium and the like), toxic heavy metals and other organic pollutants, and is a mixture with complex components and structures. The water content of the dredged sediment is generally as high as more than 75%, and the dewatering performance of the sediment is poorer along with the increase of organic matter components and charged colloids, so that whether the dredged sediment can be efficiently deeply dewatered has important influence on the subsequent treatment and disposal of the dredged sediment. The most common harmful heavy metals in the sediment comprise Pb, Zn, Ni, Cu, Cd and the like, and the heavy metals in the dredged sediment are also the main problems influencing the treatment and disposal of the heavy metals because the heavy metals cannot be decomposed and can be enriched in organisms through food chains, and the heavy metals have great harm to the natural environment and human bodies. The treatment of dredged sediment is currently mainly carried out by means of gravity (gravity thickening) or mechanical means (centrifugal thickening, belt thickening, etc.) for thickening and dewatering, by means of which dewatering is the most important reduction step of the sediment. However, these methods have disadvantages that they consume a large amount of mechanical force and power energy, and only remove free water (water which is not bound to the sediment particles, is not influenced by capillarity, and is free to flow) and intermittent water (water which is present in pores between the sediment particles or in cracks of the particles, and is bound to the particles by capillarity of the sediment), and surface-bound water (water adsorbed on the surfaces of the sediment particles due to adhesion) and cannot achieve efficient deep dehydration and reduction of the dredged sediment.
Inorganic flocculant (aluminum sulfate Al)2(SO4)3Polyaluminium chloride (PACl), organic flocculants (quaternary ammonium salts, polyamine salts, Cationic Polyacrylamide (CPAM), and the like), and composite flocculants (polyferric sulfate (PFS), Polyacrylamide (PAA), and the like) are used as common flocculants for water treatment, are used for chemical regulation and dehydration of municipal sludge or dredging sediment, mainly remove free water through electric neutralization, bridging, and the like, and cannot ensure that the flocculation dehydration effect under non-mechanical external force reaches a satisfactory effect. It has been studied to use compounds containing quaternary ammonium salt groups and long carbon chainsSilane coupling agent (3- (trimethoxysilyl) propyl-N-dodecyl dimethyl ammonium chloride), polymeric ferric sulfate and sodium dimethyl dithiocarbamate are used as raw materials to prepare covalent bond type flocculant for the research of polluted river sediment (Guolifang, covalent bond type flocculant for dehydration of dredged sediment [ D)]Beijing institute of petrochemical & 2018) compared to Al2(SO4)3CPAM and PFS, the sediment sedimentation performance is good, the water content of the test mud cake is reduced by about 14%, a better flocculation dehydration effect is realized, and the added sodium dimethyldithiocarbamate can solidify heavy metals in the sediment. However, the heavy metal content in the bottom mud concentrated and dehydrated by the method is increased and the form is stable, so that the difficulty of future safe disposal and resource utilization of the bottom mud is increased, and the heavy metal content of a resource product is easy to exceed the standard.
Similar to livestock and poultry manure, the dredged sediment is rich in nutrient substances such as nitrogen, phosphorus, organic matters and the like, and can be recycled by adopting an aerobic composting mode. The aerobic composting technology is that under aerobic condition, aerobic microorganism degrades a part of organic matters and releases energy for life activities through own catabolism, and the other part of organic matters form new cell substances through anabolism, so that the microorganism continuously proliferates. The aerobic composting technology can finally convert humus with stable property of the dredged sediment, so as to produce seedling substrate products of garden nursery stocks. However, unlike livestock and poultry manure, the river and lake dredging bottom mud treated as black and odorous water has high heavy metal content, and the heavy metal cannot be decomposed in the composting process, but the relative content of the heavy metal is increased along with the decomposition and conversion of organic matters and the like, so that the heavy metal content of the dredging bottom mud composting product is far higher than the standard value of organic matters for greening planting such as closed forest lands, expressways or forestation in the organic matrix for greening (GB/T33891 and 2017). In addition, the dredged sediment is easy to cause anaerobic fermentation and souring due to high water content, mechanical dehydration is carried out or a large amount of wood chips and other water absorbents are added to reduce the water content of the material so as to be beneficial to starting in order to meet the requirements of an aerobic composting process, and the composting cost is increased. Since the content of heavy metals in the base product is clearly specified by the country as a nursery stock base product to be applied to the environment, the heavy metals in the bottom sludge compost should not be solidified to reduce the leaching toxicity, but be considered to reduce the content (mass percentage). Hydroxyapatite is one of phosphate minerals, has an effect on heavy metals, is concerned by the environmental community, and is used as a sludge heavy metal passivator (Dengganbo, the research on the passivation and biological effectiveness of the mineral and organic materials on the heavy metals in municipal sludge [ D ] Anhui agricultural university.2015), a soil heavy metal passivator (Zhang Yongli and the like, the research on the cadmium stabilization of farmland soil by different passivators [ J ] agricultural science, 2018, 8:918-, the method comprises the steps of mixing hydroxyapatite directly into waste or using hydroxyapatite as a covering material (wrinkling in-situ covering technology research [ D ]. Shandong building university 2015) to passivate heavy metals and inhibit the release of the heavy metals. It has also been studied to compound hydroxyapatite, nano-hydroxyapatite with diatomaceous earth, monocalcium phosphate, calcium carbonate, add to the contaminated substrate sludge to carry out the solidification of heavy metals (wang hur. heavy metal contaminated substrate sludge hydroxyapatite compound immobilization technical study [ D ]. Shandong building university. 2014), and to study to combine hydroxyapatite and sodium diethyldithiocarbamate into a heavy metal fixing agent, and then to form a curing agent for the heavy metal contaminated substrate sludge (Zhonghai et al, a cadmium-copper-lead contaminated substrate sludge curing agent and a curing method therefor, ZL201610313244.4) with alkaline materials (cement, lime, fly ash), so that the leaching toxicity of heavy metals when the cured substrate sludge is finally landfilled reaches the limit of the pollution control standard for refuse landfill (GB 168892008). However, the method for curing heavy metal by adopting hydroxyapatite can not change the situation that the content of heavy metal in polluted bottom mud exceeds the standard, especially the situation that the content of heavy metal in the future resource utilization product exceeds the standard.
Disclosure of Invention
In view of the above, the invention provides a resource utilization method for river and lake dredging sediment, which aims to solve the problems that the moisture of the sediment is adjusted mechanically or by adding a large amount of conditioner in the traditional dredging sediment composting technology, and the heavy metals in the sediment are passivated by adding phosphate minerals, so that the finally prepared compost product cannot change the standard exceeding of the heavy metals in the polluted sediment.
In order to achieve the purpose, the invention provides the following technical scheme:
a resource utilization method of river and lake dredging sediment comprises the following steps:
s1, dewatering dredged sediment: adding the prepared covalent bond type composite flocculant @ Fe into dredged sediment3O4Stirring and mixing evenly for coagulation, naturally settling, removing overlying water to obtain flocculated and dewatered bottom mud, wherein Fe3O4The solid-liquid ratio of the powder to the covalent bond type composite flocculant is 1 g/L;
s2, composting the dredged sediment: adding the prepared hydroxyapatite/tobermorite @ Fe into the flocculated and dewatered bottom mud3O4The composite material is aerobically composted in an aerobically composted reactor to meet the requirement of a compost product on the maturity that the seed germination index is more than 70 percent, wherein the hydroxyapatite/tobermorite @ Fe3O4The mass ratio of the composite material to the bottom mud (dry basis) is 1: 9-2: 8;
s3, post-treatment of compost products: air-drying the composted product, performing magnetic separation, and preparing seedling culture medium from the residual humic substances and other auxiliary materials according to the formula of different seedlings.
Further, step S1 covalent bond type composite flocculant @ Fe3O4The preparation method comprises the following steps: dimethyl octadecyl [3- (triethoxysilyl) propyl group]Ammonium chloride (C)29H64ClNO3Si) and FeCl3Adding deionized water into the mixed solution, uniformly stirring to ensure that the molar ratio is 0.2-0.6, and preparing into a precursorLiquid; then the NaOH solution is dripped into the precursor liquid to reach OH-With Fe3+The molar ratio of (A) to (B) is 0.5-2, and the covalent bond type composite flocculant is prepared; finally, the ball-milled Fe3O4Adding the powder into the covalent bond type composite flocculant according to the solid-to-liquid ratio of 1g/L, and uniformly mixing to prepare the covalent bond type composite flocculant @ Fe3O4。
Further, step S1 covalent bond type composite flocculant @ Fe3O4In the preparation method of (1), dimethyloctadecyl [3- (triethoxysilyl) propyl group]Ammonium chloride and FeCl3The mixed solution is continuously stirred at the speed of 600r/min, and Fe3+The concentration is 0.2 mol/L.
Further, step S1 covalent bond type composite flocculant @ Fe3O4The preparation method of (1) is that the NaOH solution is dripped into the precursor liquid by a peristaltic pump at the speed of 6 mL/min.
Further, step S1 covalent bond type composite flocculant @ Fe3O4In the preparation method of (1), Fe after ball milling3O4The particle size of the powder is 300-400 meshes.
Further, step S1 is to add a covalent bond type composite flocculant @ Fe to the dredged sediment3O4Dredged sediment and covalent bond type composite flocculant @ Fe3O4The volume ratio of (A) to (B) is 20:1, and naturally settling for 3 h.
Further, step S2 hydroxyapatite/tobermorite @ Fe3O4The preparation method of the composite material comprises the following steps: burning egg shell at 800 deg.C for 3 hr, grinding into powder, weighing 1.1114g, adding 1.7052g of ground sodium silicate powder, adding 0.1834g of nano Fe3O4And adding 60mL of 0.1mol/L phosphoric acid solution into the powder to keep the liquid-solid ratio of the mixed system at 30mL/g, reacting for 20 hours at 200 ℃ under a hydrothermal condition, washing the product after natural cooling by using deionized water, and drying and grinding the product at 60 ℃.
Further, nano Fe in step S23O4The preparation method of the powder comprises the following steps: FeCl with the molar mass ratio of 1:2 is respectively weighed2·4H2O and FeCl3·6H2O is added to a 5mol/L NaOH solutionControlling the molar ratio of NaOH to total Fe to be 2.5:1, stirring uniformly for 2h at 80 ℃, adding concentrated nitric acid, wherein the volume ratio of the nitric acid to the NaOH solution is 0.013:1, stirring for 0.5h at 80 ℃, then adding 0.6mol/L trisodium citrate solution, wherein the volume ratio of the trisodium citrate solution to the NaOH solution is 1:1, stirring for 0.5h at 80 ℃, and cooling; magnetic separation of nano Fe from mixed liquid by magnet3O4Washing with water and drying at 60 ℃ to obtain nano Fe3O4And (3) powder.
Further, step S2 hydroxyapatite/tobermorite @ Fe3O4The particle size of the composite material after ball milling is 80-100 meshes.
Further, the composted product of step S3 is air-dried until the water content is 30%.
The invention has the beneficial effects that:
1. the invention discloses a resource utilization method of river and lake dredging sediment, which selects long carbon chains and silane coupling agents containing quaternary ammonium groups as preparation raw materials, the synthesized novel covalent bond type composite flocculant not only has the characteristics of an inorganic polymeric flocculant, but also has the characteristics of carbon functional groups, silicon functional groups and the like of the long carbon chain type organic silicon quaternary ammonium salt, and has the functions of flocculation mechanisms such as adsorption-electric neutralization, adsorption bridging, net catching, rolling and sweeping, and the organic silicon quaternary ammonium salt has the function of a surfactant and can destroy extracellular polymers of microorganisms in the sediment, so that bound water in the sediment is separated from the extracellular polymers, and the deep dehydration function is achieved. However, if the silane coupling agent is excessively added, FeCl is added at the same time3Under the acidic condition of the solution, the silicon functional group in the silane coupling agent can generate chemical reaction (such as alcoholysis reaction, redistribution reaction of the silicon functional group and the like), which is not beneficial to the preparation of the covalent bond type flocculating agent. If the addition of NaOH is excessive, the flocculant is alkaline, the molecular surface of the flocculant is rich in negative charges, and the surface of the sediment particles in the water body is also always charged with negative charges, so that electrostatic repulsion is generated, and the flocculation is influenced in an opposite effect. Thus, the silane coupling agent is bound to FeCl3In a molar ratio of 0.2 to 0.6 and OH-With Fe3+The molar ratio of (A) to (B) is 0.5-2, which not only can make the flocculant have positive charge,meanwhile, inorganic polymer and organosilicon quaternary ammonium salt can be better covalently bridged, and efficient flocculation dehydration in a short time is realized. And carrying out Fe loading by further adding a magnetic carrier3O4The magnetic carrier is used as a core, and the flocculating agent forms larger flocs with the sediment particles and is bonded with the magnetic carrier to form the magnetic flocs. In addition, the magnetic carrier can also be bridged by the flocculating agent and then is bonded with the sediment particles to form magnetic flocs. The magnetic carrier with proper particle size is selected to provide larger attached surface area, which is the key of becoming the flocculation core, and if the particle size of the magnetic floc is too small, the magnetic floc is difficult to become the core of the floc due to violent Brownian motion. If the particle size of the magnetic flocs is too large, the magnetic flocs can directly and quickly settle into the sediment under the action of gravity, and the formation of the magnetic flocs is not facilitated. Thus, Fe3O4The particle size of (A) is within a range of 300 to 400 mesh. If Fe is added excessively, Fe is added excessively3O4Not only can the amount of particles in the sediment be too much, so that the gravity sedimentation effect is dominant, even the phenomenon of layering and precipitation can occur, and the generation of magnetic flocs is not facilitated, therefore, Fe3O4The amount of (B) is preferably 1 g/L. Covalent bond type composite flocculant @ Fe3O4Not only improves the efficient flocculation dehydration of the bottom mud in a short time, but also provides possibility for promoting the heavy metal adsorption of the subsequent aerobic composting and removing the heavy metal adsorbed in the composting product.
2. The invention discloses a resource utilization method of river and lake dredging sediment, which adopts hydroxyapatite/tobermorite @ Fe3O4The composite material is used as a heavy metal adsorbent in the aerobic composting process of the flocculated bottom mud. The hexagonal columnar structure of hydroxyapatite is similar to ion exchange column, is a very ideal adsorption material, and the heavy metal ion in the water is got rid of to accessible ion exchange effect to and effects such as electrostatic absorption, dissolving precipitation, if add in the flocculation bed mud only to the heavy metal ion adsorption effect in the granule intermittent type free aquatic better, nevertheless combine not strong at the heavy metal adsorption effect on floc surface in the flocculation bed mud. The tobermorite mineral has a structure similar to that of amorphous C-S-H, and is mainly based onHeavy metal ions into the crystal lattice to dissociate Ca2+And removing heavy metal ions by replacement, and compounding the two on the basis of a compounding process to prepare the hydroxyapatite/tobermorite composite material so as to enhance the capability of the hydroxyapatite for adsorbing the heavy metals on the surface of the sediment particles. Then the hydroxyapatite/tobermorite composite material is doped with Fe, which is because of Fe0The (zero-valent iron) doping can not improve the heavy metal adsorption capacity of tobermorite, and only Al replaces the doping to improve the adsorption performance of tobermorite, so that the doping of magnetic nano Fe3O4(Fe (II), Fe (III)) based on doped nano-Fe3O4Can be used as covalent bond type composite flocculant @ Fe3O4The magnetic flocs in the material are attracted by the magnetic attraction effect, so that the hydroxyapatite/tobermorite @ Fe is increased3O4The composite material is contacted with the surface of the sediment particles, so that the adsorption of the composite material on the heavy metal on the surface of the flocculated sediment particles is improved. Thus, in one aspect, doping with Fe3O4The method achieves the effect of flocculating the 'bridging' between the sediment particles and the hydroxyapatite/tobermorite composite powder for the magnetic covalent bond type composite flocculant, realizes the efficient adsorption of heavy metals on the composite, and provides possibility for removing the heavy metals adsorbed on the composite through the magnetic separation of the compost decomposed product after the decomposition of organic matters, thereby reducing the content of the heavy metals in the compost product. Moreover, the hydroxyapatite-based composite material may also provide a carrier for growth and metabolism of microorganisms of the composting process.
3. The resource utilization method of the river and lake dredging sediment, disclosed by the invention, firstly carries out deep flocculation dehydration through a covalent bond type composite flocculant containing a magnetic carrier, and after the magnetic carrier is added, due to the generation of magnetic floc, the possibility is provided for realizing that heavy metals adsorbed on the surface of sediment particles are adsorbed by a composite adsorbent in the subsequent composting process and further separating compost materials through subsequent magnetic separation. Secondly, adding hydroxyapatite/tobermorite @ Fe into the flocculation dehydration bottom mud composting process3O4The composite material is used as heavy metal adsorbent, and hydroxyapatite is used as heavy metal adsorbentThe agent is used for aerobic composting of bottom mud, the adsorption capacity of the agent on heavy metals on the surfaces of particles is enhanced by compounding tobermorite, and nano Fe is doped3O4So as to strengthen the acting force of the composite material on the mud particles in the magnetic floccule, thereby realizing the high-efficiency adsorption of the composite material on the heavy metal. Finally, the heavy metals in the air-dried compost decomposed material can follow hydroxyapatite/tobermorite @ Fe3O4The composite material is removed from the material by magnetic separation, thereby reducing the content of heavy metals in the product. Compared with the direct aerobic composting treatment, the resource utilization method of the river and lake dredging sediment overcomes the problems of large difficulty in dehydration pretreatment and difficulty in reaching the standard of the quality of the product due to high heavy metal, and the quality of the composting product can meet the standard value (level II) of organic matters for greening planting in a closed forest land, a freeway or afforestation and the like in an organic matrix for greening (GB/T33891-2017).
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a process flow chart of the resource utilization method of river and lake dredging sediment.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Wherein the showings are for the purpose of illustrating the invention only and not for the purpose of limiting the same, and in which there is shown by way of illustration only and not in the drawings in which there is no intention to limit the invention thereto; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The same or similar reference numerals in the drawings of the embodiments of the present invention correspond to the same or similar components; in the description of the present invention, it should be understood that if there is an orientation or positional relationship indicated by terms such as "upper", "lower", "left", "right", "front", "rear", etc., based on the orientation or positional relationship shown in the drawings, it is only for convenience of description and simplification of description, but it is not an indication or suggestion that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and therefore, the terms describing the positional relationship in the drawings are only used for illustrative purposes, and are not to be construed as limiting the present invention, and the specific meaning of the terms may be understood by those skilled in the art according to specific situations.
The river and lake dredging sediment is rich in organic substances, can be used for preparing seedling raising substrates after humification of aerobic compost, and realizes resource utilization, but the dredging sediment cannot be directly used for the aerobic compost due to high water content, and the conventional flocculating agent and the covalent bond type flocculating agent still have the problems that the flocculation dehydration effect is to be improved, and heavy metals cannot be removed due to solidification.
Comparative example
Dredged sediment is naturally settled and then directly subjected to traditional aerobic composting, air drying and magnetic separation are not carried out, and dredged sediment collected in the same batch and not subjected to any treatment is adopted as a reference material (namely, the dredged sediment is not subjected to flocculation dehydration and added with hydroxyapatite/tobermorite @ Fe @ in the comparative examples and the examples 1-3)3O4Composite material), only naturally settled for 3h to dehydrate, and then according to the sameIn examples 1 to 3, aerobic composting was carried out with the same composting parameters (e.g., type of composting reactor, oxygen supply parameters, number of days for composting, etc.), and the parameters related to the compost material were measured and shown in table 1.
Example 1
As shown in fig. 1, a resource utilization method of river and lake dredging sediment comprises the following steps:
s1, dewatering dredged sediment: adding the prepared covalent bond type composite flocculant @ Fe into dredged sediment3O4Uniformly stirring and mixing the mixture, coagulating the mixture, naturally settling the mixture, and removing overlying water to obtain flocculated and dewatered bottom mud;
the method specifically comprises the following steps: s11, preparation of the composite flocculant precursor liquid: dimethyl octadecyl [3- (triethoxysilyl) propyl group]Ammonium chloride (molecular formula C)29H64ClNO3Si) and FeCl3Mixing according to the molar ratio of 0.2, adding a certain amount of deionized water to ensure that Fe is contained in the mixture3+Dimethyl octadecyl [3- (triethoxysilyl) propyl ] with a concentration of 0.2mol/L]The concentration of ammonium chloride is 0.04mol/L, and the solution is continuously stirred at the speed of 600r/min to prepare precursor solution;
s12, preparation of covalent bond type composite flocculant: taking 1L of the precursor liquid prepared in the step S11, and dropwise adding 200mL of 0.5mol/L NaOH solution into the precursor liquid at the speed of 6mL/min by using a peristaltic pump to obtain OH-With Fe3+The molar ratio of the flocculant to the water is 0.5, and the covalent bond type composite flocculant is prepared;
s13 covalent bond type composite flocculant @ Fe3O4The preparation of (1): ball milled Fe3O4The particle size of the powder is between 300 and 400 meshes, and Fe is added3O4Adding the powder into the covalent bond type composite flocculant prepared in the step S12 according to the solid-to-liquid ratio of 1g/L, and uniformly mixing to prepare the covalent bond type composite flocculant @ Fe3O4；
S14, dewatering dredged sediment: adding 5L of covalent bond type composite flocculant @ Fe prepared in step S13 into 100L of dredged sediment3O4Stirring and mixing evenly for coagulation, naturally settling for 3h, removing the overlying water to obtain flocculated and dewatered productThe bottom mud of (1).
S2, composting the dredged sediment: adding the prepared hydroxyapatite/tobermorite @ Fe into the flocculated and dewatered bottom mud3O4The composite material is aerobically composted in an aerobically composting reactor to meet the requirement of the maturity that the germination index of seeds of compost products is more than 70 percent (NY/T525-2021);
the method specifically comprises the following steps: s21, nano Fe3O4Preparation of powder: 1.99g FeCl was weighed out separately2·4H2O、5.41g FeCl3·6H2Adding O with the molar mass ratio of 1:2 into 15mL of 5mol/L NaOH solution, namely the molar ratio of NaOH to total Fe is 2.5:1, stirring uniformly for 2h at 80 ℃, then adding 0.195mL of concentrated nitric acid, namely the volume ratio of nitric acid to NaOH solution is 0.013:1, stirring for 0.5h at 80 ℃, then adding 15mL of 0.6mol/L trisodium citrate solution, namely the volume ratio of the trisodium citrate solution to the NaOH solution is 1:1, stirring for 0.5h at 80 ℃, and cooling. Magnetic separation of nano Fe from mixed liquid by magnet3O4Washing with water and drying at 60 ℃ to obtain about 6.9g of nano Fe3O4Powder;
s22 hydroxyapatite/tobermorite @ Fe3O4Preparing a composite material: burning egg shell at 800 deg.C for 3 hr, grinding into powder, weighing 1.1114g, adding 1.7052g of ground sodium silicate powder, adding 0.1834g of nano Fe prepared in step S213O4Adding 60mL of 0.1mol/L phosphoric acid solution into the powder to keep the liquid-solid ratio of a mixed system at 30mL/g, reacting for 20 hours at 200 ℃ under a hydrothermal condition, washing a product after natural cooling by using deionized water, and drying at 60 ℃ to obtain 1.9189g of hydroxyapatite/tobermorite @ Fe3O4Grinding the composite material into particles with the particle size of 80-100 meshes;
s23, composting the dredged sediment: adding the hydroxyapatite/tobermorite @ Fe prepared in the step S22 into the flocculated and dewatered bottom mud3O4Composite material, hydroxyapatite/tobermorite @ Fe3O4The mass ratio of the composite material to the bottom mud (dry basis) is 1:9, and aerobic composting is carried out in an aerobic composting reactor to meet the composting productionThe seed germination index of the product is more than 70 percent (NY/T525-2021) of the requirement of the maturity.
S3, post-treatment of compost products: air-drying the composted product until the water content is about 30%, performing magnetic separation, wherein the residual humic substances can reach the heavy metal standard value of organic matters for greening planting, such as closed forest lands, expressways or afforestation, in an organic substrate for greening (GB/T33891-2017), and then preparing the organic matters and other auxiliary materials into a seedling culture substrate according to the formula of different seedlings.
Example 1 aerobic composting was carried out according to the same composting parameters as the control examples (e.g. type of composting reactor, oxygen supply parameters, days of composting etc.) and the relevant parameters of the composting material were determined and are shown in table 1.
Dredged sediment is treated by the method of the embodiment 1, and the sediment is added with covalent bond type composite flocculant @ Fe3O4After flocculation and natural sedimentation for 3h, the water content of the bottom mud is measured to be reduced from the initial 83.1 percent to 66.6 percent and reduced by 16.5 percent, while the covalent bond type composite flocculant @ Fe is added in the comparative example3O4After the flocculation is naturally settled for 3 hours, the water content of the bottom mud is measured to be reduced from 83.1 percent to 79.3 percent initially and is reduced by 3.8 percent only, so that the dehydration effect can be improved by 12.7 percent compared with that of a control example; moreover, the water content of the compost product after the aerobic composting of the efficiently dehydrated bottom mud in the example 1 is reduced to 48.1%, which is reduced by 14.7% compared with the water content (62.8%) of the compost product after the composting is finished under the control of the same aerobic composting process parameters, which not only indicates that the water content of the compost product in the example 1 is in the range of the water content with normal humus (40% -50%), but also verifies that the excessively high water content (62.8%) of the compost product in the comparative example indicates that the compost product is not an excellent aerobic composting process product, and actually contains anaerobic fermentation products (namely biogas residues containing a certain amount of biogas slurry) caused by the blockage of gaps under the high water content.
In addition, in the comparative example, the dredged sediment is directly composted after being naturally settled and is converted into CO along with the degradation of organic substances2、H2The relative contents of O and heat are reduced due to the isoloss of O and heat, and heavy metal phases in the product are generatedOn the dry basis, the content of the main heavy metals (on the dry basis) of the product (humic substance) obtained by the composting process, air drying and magnetic separation in example 1 is slightly increased, while the content of the main heavy metals (on the dry basis) of the product (humic substance) obtained by the composting process is respectively 283mg/kg, 2.56mg/kg, 2.28mg/kg, 16.6mg/kg and 176mg/kg of the total lead, total cadmium, total mercury, total arsenic and total chromium in comparison with the initial heavy metal content (on the dry basis) of the dredging bottom mud is respectively reduced by 48.8 percent, 62.4 percent, 56.8 percent, 58.9 percent and 55.6 percent which are respectively lower than the standard value (level II) in the greening organic matrix (GB/T33891 and 2017), namely the limit value of the content of the heavy metals (300 mg/kg, 3.0mg/kg, 20mg/kg and 200mg/kg) for greening planting in the closed forest land, expressway or afforestation is met, therefore, the seedling raising substrate can be prepared by the seedling raising substrate and other auxiliary materials according to different seedling requirement formulas.
Example 2
As shown in fig. 1, a method for resource utilization of river and lake dredging sediment comprises the following steps:
s1, dewatering dredged sediment: adding the prepared covalent bond type composite flocculant @ Fe into dredged sediment3O4Uniformly stirring and mixing the mixture, coagulating the mixture, naturally settling the mixture, and removing overlying water to obtain flocculated and dewatered bottom mud;
the method specifically comprises the following steps: s11, preparation of the composite flocculant precursor liquid: dimethyl octadecyl [3- (triethoxysilyl) propyl group]Ammonium chloride (molecular formula C)29H64ClNO3Si) and FeCl3Mixing according to the molar ratio of 0.4, adding a certain amount of deionized water to ensure that Fe is contained in the mixture3+Dimethyl octadecyl [3- (triethoxysilyl) propyl ] with a concentration of 0.2mol/L]The concentration of ammonium chloride is 0.08mol/L, and the mixture is continuously stirred at the speed of 600r/min to prepare precursor liquid;
s12, preparation of covalent bond type composite flocculant: taking 1L of the precursor liquid prepared in the step S11, and dropwise adding 400mL of 0.5mol/L NaOH solution into the precursor liquid at the speed of 6mL/min by using a peristaltic pump to obtain OH-With Fe3+The molar ratio of the flocculant to the water is 1, and the covalent bond type composite flocculant is prepared;
s13 covalent bond type composite flocculant @ Fe3O4The preparation of (1): ball milled Fe3O4The particle size of the powder is 300-400 meshes, and then Fe is added3O4Adding the powder into the covalent bond type composite flocculant prepared in the step S12 according to the solid-to-liquid ratio of 1g/L, and uniformly mixing to prepare the covalent bond type composite flocculant @ Fe3O4；
S14, dewatering dredged sediment: adding 5L of covalent bond type composite flocculant @ Fe prepared in step S13 into 100L of dredged sediment3O4Stirring and mixing uniformly, coagulating, naturally settling for 3h, and removing the overlying water to obtain the flocculated and dewatered bottom mud.
S2, composting the dredged sediment: adding the prepared hydroxyapatite/tobermorite @ Fe into the flocculated and dewatered bottom mud3O4The composite material is aerobically composted in an aerobically composting reactor to meet the requirement of the maturity that the germination index of seeds of compost products is more than 70 percent (NY/T525-2021);
the method specifically comprises the following steps: s21, nano Fe3O4Preparation of powder: 1.99g FeCl was weighed out separately2·4H2O、5.41g FeCl3·6H2Adding O with the molar mass ratio of 1:2 into 15mL of 5mol/L NaOH solution, namely the molar ratio of NaOH to total Fe is 2.5:1, stirring uniformly for 2h at 80 ℃, then adding 0.195mL of concentrated nitric acid, namely the volume ratio of nitric acid to NaOH solution is 0.013:1, stirring for 0.5h at 80 ℃, then adding 15mL of 0.6mol/L trisodium citrate solution, namely the volume ratio of the trisodium citrate solution to the NaOH solution is 1:1, stirring for 0.5h at 80 ℃, and cooling. Magnetic separation of nano Fe from mixed liquid by magnet3O4Washing with water and drying at 60 ℃ to obtain about 6.9g of nano Fe3O4Powder;
s22 hydroxyapatite/tobermorite @ Fe3O4Preparing a composite material: burning egg shell at 800 deg.C for 3 hr, grinding into powder, weighing 1.1114g, adding 1.7052g of ground sodium silicate powder, adding 0.1834g of nano Fe prepared in step S213O4Adding 0.1mol/L phosphoric acid solution 60mL to maintain the liquid-solid ratio of the mixed system at 30mL/g, and adding water at 200 deg.CReacting for 20h under the thermal condition, washing the product after natural cooling by using deionized water, and drying at 60 ℃ to obtain about 1.9189g of hydroxyapatite/tobermorite @ Fe3O4Grinding the composite material into particles with the particle size of 80-100 meshes;
s23, composting the dredged sediment: adding the hydroxyapatite/tobermorite @ Fe prepared in the step S22 into the flocculated and dewatered bottom mud3O4Composite material, hydroxyapatite/tobermorite @ Fe3O4The mass ratio of the composite material to the bottom mud (dry basis) is 1.5:8.5, and aerobic composting is carried out in an aerobic composting reactor to meet the requirement of the maturity of a compost product that the seed germination index is more than 70% (NY/T525-2021);
s3, post-treatment of compost products: air-drying the composted product until the water content is about 30%, performing magnetic separation, wherein the residual humic substances can reach the heavy metal standard value of organic matters for greening planting, such as closed forest lands, expressways or afforestation, in an organic substrate for greening (GB/T33891-2017), and then preparing the organic matters and other auxiliary materials into a seedling culture substrate according to the formula of different seedlings.
Example 2 aerobic composting was carried out according to the same composting parameters as the control examples (e.g. type of composting reactor, oxygen supply parameters, days of composting etc.) and the relevant parameters of the composting material were determined and are shown in table 1.
Dredged sediment was treated as in example 2, by adding a covalent bond type composite flocculant @ Fe3O4After flocculation and natural sedimentation for 3h, the water content of the bottom mud is measured to be reduced from 83.1 percent to 63.2 percent initially and reduced by 19.9 percent, while the covalent bond type composite flocculant @ Fe is added in the comparative example3O4After the flocculation is naturally settled for 3 hours, the water content of the bottom mud is measured to be reduced from 83.1 percent to 79.3 percent initially and is reduced by 3.8 percent only, so that the dewatering effect can be improved by 16.1 percent compared with that of a control example; moreover, in example 1, the water content of the compost product at the end of aerobic composting of the efficiently dehydrated sediment is reduced to 46.6%, which is 16.2% lower than the water content (62.8%) of the compost product at the end of composting under the control of the same aerobic composting process parametersThis not only indicates that the water content of the compost product in example 1 is in the range of the water content with normal humus (40% -50%), but also verifies that the water content of the compost product which is too high in the comparative example (62.8%) indicates that the compost product is not a good aerobic compost process product, and indeed contains anaerobic fermentation products (i.e. biogas residues containing a certain amount of biogas slurry) which are partially caused by the blockage of gaps under the high water content.
In addition, in the comparative example, the dredged sediment is directly composted after being naturally settled and is converted into CO along with the degradation of organic substances2、H2The relative contents of O and heat are reduced by equal dissipation, which results in that the relative contents (on a dry basis) of heavy metals in the product are slightly increased, while the contents (on a dry basis) of main heavy metals in the product (humic substance) obtained by the composting process, air drying and magnetic separation in example 1 are respectively reduced by 60.9%, 73.1%, 68.9%, 74.8% and 66.2% compared with the initial heavy metal content (on a dry basis) of the dredged sediment, which are respectively lower than the standard value (level II) of the greening organic matrix (GB/T33891) and 2017, namely the heavy metal content of the greening planting organic matter for closing the forest land, the highway or the afforestation is less than the limit value (300 mg/kg, 134 mg/kg), Less than or equal to 3.0mg/kg, less than or equal to 20mg/kg and less than or equal to 200mg/kg), so that the seedling culture substrate can be prepared by the seedling culture substrate and other auxiliary materials according to different seedling requirement formulas.
Example 3
As shown in fig. 1, a method for resource utilization of river and lake dredging sediment comprises the following steps:
s1, dewatering dredged sediment: adding the prepared covalent bond type composite flocculant @ Fe into dredged sediment3O4Uniformly stirring and mixing the mixture, coagulating the mixture, naturally settling the mixture, and removing overlying water to obtain flocculated and dewatered bottom mud;
the method specifically comprises the following steps: s11, preparation of the composite flocculant precursor liquid: dimethyl octadecyl [3- (triethoxysilyl) propyl group]Ammonium chloride (molecular formula C)29H64ClNO3Si) and FeCl3Mixing according to a molar ratio of 0.6, addingDeionized water in a fixed amount to make Fe contained therein3+Dimethyl octadecyl [3- (triethoxysilyl) propyl ] with a concentration of 0.2mol/L]The concentration of ammonium chloride is 0.12mol/L, and the mixture is continuously stirred at the speed of 600r/min to prepare precursor liquid;
s12, preparation of covalent bond type composite flocculant: taking 1L of the precursor liquid prepared in the step S11, and dropwise adding 800mL of 0.5mol/L NaOH solution into the precursor liquid at the speed of 6mL/min by using a peristaltic pump to obtain OH-With Fe3+The molar ratio of the flocculant to the water is 2, and the covalent bond type composite flocculant is prepared;
s13 covalent bond type composite flocculant @ Fe3O4The preparation of (1): ball milled Fe3O4The particle size of the powder is 300-400 meshes, and then Fe is added3O4Adding the powder into the covalent bond type composite flocculant prepared in the step S12 according to the solid-to-liquid ratio of 1g/L, and uniformly mixing to prepare the covalent bond type composite flocculant @ Fe3O4；
S14, dewatering dredged sediment: adding 5L of covalent bond type composite flocculant @ Fe prepared in step S13 into 100L of dredged sediment3O4Stirring and mixing uniformly, coagulating, naturally settling for 3h, and removing the overlying water to obtain the flocculated and dewatered bottom mud.
S2, composting the dredged sediment: adding the prepared hydroxyapatite/tobermorite @ Fe into the flocculated and dewatered bottom mud3O4The composite material is aerobically composted in an aerobically composting reactor to meet the requirement of the maturity that the germination index of seeds of compost products is more than 70 percent (NY/T525-2021);
the method specifically comprises the following steps: s21, nano Fe3O4Preparation of powder: 1.99g FeCl was weighed out separately2·4H2O、5.41g FeCl3·6H2O with the molar mass ratio of 1:2 is added into 15mL of 5mol/L NaOH solution, namely the molar ratio of NaOH to total Fe is 2.5:1, the mixture is stirred evenly for 2h at 80 ℃, then 0.195mL of concentrated nitric acid is added, namely the volume ratio of the nitric acid to the NaOH solution is 0.013:1, the mixture is stirred for 0.5h at 80 ℃, then 15mL of 0.6mol/L trisodium citrate solution is added, namely the volume ratio of the trisodium citrate solution to the NaOH solutionStirring at 80 ℃ for 0.5h for 1:1, and cooling. Magnetic separation of nano Fe from mixed liquid by magnet3O4Washing with water and drying at 60 ℃ to obtain about 6.9g of nano Fe3O4Powder;
s22 hydroxyapatite/tobermorite @ Fe3O4Preparing a composite material: burning egg shell at 800 deg.C for 3 hr, grinding into powder, weighing 1.1114g, adding 1.7052g of ground sodium silicate powder, adding 0.1834g of nano Fe prepared in step S213O4Adding 60mL of 0.1mol/L phosphoric acid solution into the powder to keep the liquid-solid ratio of a mixed system at 30mL/g, reacting for 20 hours at 200 ℃ under a hydrothermal condition, washing a product after natural cooling by using deionized water, and drying at 60 ℃ to obtain 1.9189g of hydroxyapatite/tobermorite @ Fe3O4Grinding the composite material into particles with the particle size of 80-100 meshes;
s23, composting the dredged sediment: adding the hydroxyapatite/tobermorite @ Fe prepared in the step S22 into the flocculated and dewatered bottom mud3O4Composite material, hydroxyapatite/tobermorite @ Fe3O4The mass ratio of the composite material to the bottom mud (dry basis) is 2:8, and aerobic composting is carried out in an aerobic composting reactor to meet the requirement of the seed germination index of a compost product being more than 70% (NY/T525-2021) on the degree of maturity.
S3, post-treatment of compost products: air-drying the composted product until the water content is about 30%, performing magnetic separation, wherein the residual humic substances can reach the heavy metal standard value of organic matters for greening planting, such as closed forest lands, expressways or afforestation, in an organic substrate for greening (GB/T33891-2017), and then preparing the organic matters and other auxiliary materials into a seedling culture substrate according to the formula of different seedlings.
Example 3 aerobic composting was carried out according to the same composting parameters as the control examples (e.g. type of composting reactor, oxygen supply parameters, days of composting etc.) and the relevant parameters of the composting material were determined and are shown in table 1.
Dredged sediment is treated by the method in the embodiment 3, and the sediment is added with covalent bond type composite flocculant @ Fe3O4Flocculating and naturally settling for 3hWhen the water content of the bottom mud is measured to be reduced to 60.8 percent from 83.1 percent initially, the water content is reduced by 22.3 percent, and the covalent bond type composite flocculant @ Fe is added into the comparative example3O4After the flocculation is naturally settled for 3 hours, the water content of the bottom mud is measured to be reduced from 83.1 percent to 79.3 percent initially and is reduced by 3.8 percent only, so that the dehydration effect can be improved by 18.5 percent compared with that of a control example; moreover, in example 1, the water content of the compost product after the aerobic composting of the efficiently dehydrated bottom mud is finished is reduced to 45.4%, which is reduced by 17.4% compared with the water content (62.8%) of the compost product after the composting is finished under the control of the same aerobic composting process parameters, which not only indicates that the water content of the compost product in example 1 is in the range of the water content with normal humus (40% -50%), but also verifies that the excessively high water content (62.8%) of the compost product in the comparative example indicates that the compost product is not an excellent aerobic composting process product, and actually contains anaerobic fermentation products (namely biogas residues containing a certain amount of biogas slurry) caused by the blockage of gaps under high water content.
In addition, in the comparative example, the dredged sediment is directly composted after being naturally settled and is converted into CO along with the degradation of organic substances2、H2The relative contents of O and heat are reduced by equal dissipation, which results in that the relative contents (on a dry basis) of heavy metals in the product are slightly increased, while the contents (on a dry basis) of main heavy metals in the product (humic substance) obtained by the composting process, air drying and magnetic separation in example 1 are respectively 162mg/kg, 1.14mg/kg, 1.05mg/kg, 8.13mg/kg and 101mg/kg of total lead, total cadmium, total mercury, total arsenic and total chromium, which are respectively reduced by 70.7%, 83.3%, 80.1%, 79.9% and 74.5% compared with the initial heavy metal content (on a dry basis) of the dredged sediment, which are respectively lower than the standard value (level II) of the greening organic matrix (GB/T33891) and 2017), namely the heavy metal content limit (300 mg/kg, or less than the limit of the organic matter for greening planting such as forest land closure, highway or afforestation is satisfied, Less than or equal to 3.0mg/kg, less than or equal to 20mg/kg and less than or equal to 200mg/kg), so that the seedling culture substrate can be prepared by the seedling culture substrate and other auxiliary materials according to different seedling requirement formulas.
Table 1 effect of resource utilization of river and lake dredging sediment in each example
In conclusion, the resource utilization method of the river and lake dredging sediment, which is designed by the method, firstly carries out deep flocculation dehydration through the covalent bond type composite flocculant containing the magnetic carrier, and the added magnetic carrier provides possibility for realizing that the heavy metal adsorbed on the surface of sediment particles is adsorbed by the composite adsorbent in the subsequent composting process and further separating compost materials through subsequent magnetic separation due to the generation of magnetic floc. Secondly, adding hydroxyapatite/tobermorite @ Fe into the flocculation dehydration bottom mud composting process3O4The composite material is subjected to heavy metal adsorbent, hydroxyapatite is used as the heavy metal adsorbent for aerobic composting of bottom mud, the adsorption capacity of the composite tobermorite on heavy metal on the particle surface is enhanced by compounding the tobermorite, and nano Fe is doped3O4So as to strengthen the acting force of the composite material on the mud particles in the magnetic floccule, thereby realizing the high-efficiency adsorption of the composite material on the heavy metal. Finally, the heavy metals in the air-dried compost decomposed material can follow hydroxyapatite/tobermorite @ Fe3O4The composite material is removed from the material by magnetic separation, thereby reducing the content of heavy metals in the product.
Compared with the method for directly carrying out aerobic composting, the resource utilization method of river and lake dredging sediment designed by the method overcomes the problems of large difficulty in dehydration pretreatment and difficulty in reaching the standard of the quality of the product due to high heavy metal, and the quality of the compost product can meet the standard value (level II) of organic matters for greening planting in an organic matrix for greening (GB/T33891-2017) for closing forest lands, expressways or forestation and the like.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. A resource utilization method of river and lake dredging sediment is characterized by comprising the following steps:
s1, dewatering dredged sediment: adding the prepared covalent bond type composite flocculant @ Fe into dredged sediment3O4Stirring and mixing evenly for coagulation, naturally settling, removing overlying water to obtain flocculated and dewatered bottom mud, wherein Fe3O4The solid-liquid ratio of the powder to the covalent bond type composite flocculant is 1 g/L;
s2, composting the dredged sediment: adding the prepared hydroxyapatite/tobermorite @ Fe into the flocculated and dewatered bottom mud3O4The composite material is aerobically composted in an aerobically composted reactor to meet the requirement of a compost product on the maturity that the seed germination index is more than 70 percent, wherein the hydroxyapatite/tobermorite @ Fe3O4The mass ratio of the composite material to the bottom mud (dry basis) is 1: 9-2: 8;
s3, post-treatment of compost products: air-drying the composted product, performing magnetic separation, and preparing seedling culture medium from the residual humic substances and other auxiliary materials according to the formula of different seedlings.
2. The resource utilization method of river and lake dredging sediment as claimed in claim 1, wherein the step S1 is that the covalent bond type composite flocculant @ Fe3O4The preparation method comprises the following steps: dimethyl octadecyl [3- (triethoxysilyl) propyl group]Ammonium chloride (C)29H64ClNO3Si) and FeCl3Adding deionized water into the mixed solution, uniformly stirring to enable the molar ratio of the mixed solution to be 0.2-0.6, and preparing into precursor liquid; then the NaOH solution is dripped into the precursor liquid to reach OH-With Fe3+The molar ratio of (A) to (B) is 0.5-2, and the covalent bond type composite flocculant is prepared; finally, the ball-milled Fe3O4Adding the powder into the covalent bond type composite flocculant according to the solid-to-liquid ratio of 1g/L, and uniformly mixing to prepare the covalent bond type composite flocculant @ Fe3O4。
3. The resource utilization method of river and lake dredging sediment as claimed in claim 2, wherein the step S1 is that the covalent bond type composite flocculant @ Fe3O4In the preparation method of (1), dimethyloctadecyl [3- (triethoxysilyl) propyl group]Ammonium chloride and FeCl3The mixed solution is continuously stirred at the speed of 600r/min, and Fe3+The concentration is 0.2 mol/L.
4. The resource utilization method of river and lake dredging sediment as claimed in claim 2, wherein the step S1 is that the covalent bond type composite flocculant @ Fe3O4The preparation method of (1) is that the NaOH solution is dripped into the precursor liquid by a peristaltic pump at the speed of 6 mL/min.
5. The resource utilization method of river and lake dredging sediment as claimed in claim 2, wherein the step S1 is that the covalent bond type composite flocculant @ Fe3O4In the preparation method of (1), Fe after ball milling3O4The particle size of the powder is 300-400 meshes.
6. The resource utilization method of river and lake dredged sediment according to claim 1, wherein the step S1 is to add covalent bond type composite flocculant @ Fe to the dredged sediment3O4Dredged sediment and covalent bond type composite flocculant @ Fe3O4The volume ratio of (A) to (B) is 20:1, and naturally settling for 3 h.
7. The resource utilization method of river and lake dredging sediment as claimed in claim 1, wherein the step S2 hydroxyapatite/tobermorite @ Fe3O4The preparation method of the composite material comprises the following steps: burning egg shell at 800 deg.C for 3 hr, grinding into powder, weighing 1.1114g, adding 1.7052g of ground sodium silicate powder, adding 0.1834g of nano Fe3O4And adding 60mL of 0.1mol/L phosphoric acid solution into the powder to keep the liquid-solid ratio of the mixed system at 30mL/g, reacting for 20 hours at 200 ℃ under a hydrothermal condition, washing the product after natural cooling by using deionized water, and drying and grinding the product at 60 ℃.
8. The resource utilization method of river and lake dredging sediment as claimed in claim 7, wherein the step S2 is performed by using nano Fe3O4The preparation method of the powder comprises the following steps: FeCl with the molar mass ratio of 1:2 is respectively weighed2·4H2O and FeCl3·6H2Adding O into 5mol/L NaOH solution, controlling the molar ratio of NaOH to total Fe to be 2.5:1, stirring uniformly at 80 ℃ for 2h, adding concentrated nitric acid, wherein the volume ratio of the nitric acid to the NaOH solution is 0.013:1, stirring at 80 ℃ for 0.5h, then adding 0.6mol/L trisodium citrate solution, the volume ratio of the trisodium citrate solution to the NaOH solution is 1:1, stirring at 80 ℃ for 0.5h, and cooling; magnetic separation of nano Fe from mixed liquid by magnet3O4Washing with water and drying at 60 ℃ to obtain nano Fe3O4And (3) powder.
9. The resource utilization method of river and lake dredging sediment as claimed in claim 1, wherein the step S2 hydroxyapatite/tobermorite @ Fe3O4The particle size of the composite material after ball milling is 80-100 meshes.
10. The resource utilization method of river and lake dredging sediment as claimed in claim 1, wherein the product after composting in step S3 is air-dried until the water content is 30%.
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