CN117085641A - Heavy metal adsorbent in solid-waste pyrolysis process and preparation and use methods thereof - Google Patents
Heavy metal adsorbent in solid-waste pyrolysis process and preparation and use methods thereof Download PDFInfo
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- CN117085641A CN117085641A CN202311217994.8A CN202311217994A CN117085641A CN 117085641 A CN117085641 A CN 117085641A CN 202311217994 A CN202311217994 A CN 202311217994A CN 117085641 A CN117085641 A CN 117085641A
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- heavy metal
- metal adsorbent
- phosphate
- pyrolysis
- kaolin
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 127
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 49
- 239000003463 adsorbent Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 20
- 239000002910 solid waste Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 27
- 239000010452 phosphate Substances 0.000 claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 26
- 238000005470 impregnation Methods 0.000 claims abstract description 15
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 claims abstract description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 31
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 31
- 239000010813 municipal solid waste Substances 0.000 claims description 29
- 235000012211 aluminium silicate Nutrition 0.000 claims description 27
- 239000000654 additive Substances 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 15
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 15
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 235000011008 sodium phosphates Nutrition 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010433 feldspar Substances 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- -1 phosphate anions Chemical class 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000002296 pyrolytic carbon Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 235000019983 sodium metaphosphate Nutrition 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003077 quantum chemistry computational method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/10—Destroying solid waste or transforming solid waste into something useful or harmless involving an adsorption step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a heavy metal adsorbent in a solid waste pyrolysis process and a preparation and use method thereof, and relates to the field of pollutant control of solid waste pyrolysis treatment. The heavy metal adsorbent comprises phosphate and aluminosilicate/aluminosilicate minerals, wherein the impregnation ratio of the phosphate to the aluminosilicate/aluminosilicate minerals is 2.5% -30%, and the mass concentration of the phosphate is 4.17-50 g/L.
Description
Technical Field
The invention relates to the field of pollutant control of solid waste pyrolysis treatment, in particular to a heavy metal adsorbent in a solid waste pyrolysis process and a preparation and use method thereof.
Background
The household garbage pyrolysis can effectively reduce the generation of dioxin and the biotoxicity of heavy metal Cr, combines the garbage treatment technology with the carbon storage technology, and is an important development direction of urban garbage treatment in the future under the current global climate accelerating and warming environment.
Common household garbage such as glass, plastic, inert materials and the like contains high heavy metals, cr in rubber can reach 700mg/kg of dry garbage, and the heavy metals in the garbage are gradually valued by people due to the characteristics of strong mobility, difficult degradation, high hazard and the like, wherein As, cd, cr, pb is four of heavy metal five toxins and has the greatest hazard effect on human bodies.
The method for removing the volatile heavy metals in the garbage treatment process mainly comprises three methods, namely a technology before heat treatment, a technology for treating the tail gas during heat treatment and a technology for treating the tail gas. The garbage classification in China is still in a starting stage at present, the heavy metal content in other garbage after classification is high, the garbage classification can not fully recover the heavy metal, and the problem of heavy metal control still needs to be considered in the subsequent treatment. At present, the heavy metal is removed in the garbage heat treatment process mainly by a tail gas treatment technology, the aim of reducing the heavy metal content of the tail gas is achieved by optimizing a tail gas purification system and a combination, no purification equipment which is matched with the tail gas for removing the heavy metal is available in the industry, but the conventional tail gas treatment system such as a bag-type dust remover, a denitration and desulfurization device, activated carbon spray adsorption and the like has a certain removal effect on the heavy metal in the tail gas. When the tail gas treatment system is used for controlling heavy metals, the heavy metals can affect the denitration catalyst and the desulfurization gypsum, and the adsorption cost is higher by using the activated carbon.
The technology for controlling the additive in the furnace of the heavy metals is to adopt the additive to fix most of the heavy metals in pyrolysis residues in the pyrolysis process of the domestic garbage. On one hand, the pressure of subsequent tail gas treatment equipment is reduced, the influence on the quality of pyrolysis gas pyrolysis oil is reduced, on the other hand, the heavy metal cannot disappear due to the heavy metal treatment technology, and finally, the heavy metal is enriched for subsequent treatment, and the heavy metal is trapped in the pyrolytic carbon through the in-furnace additive, so that the purpose of enriching the heavy metal is achieved, and the subsequent unified treatment of the heavy metal is facilitated.
For the technology of controlling heavy metals in a furnace in the solid waste heat treatment process, researchers also provide a plurality of methods:
patent CN 112741979B describes an in-furnace additive for adsorbing heavy metal arsenic in the pyrolysis process of municipal solid waste, which is mainly prepared by modifying kaolin with nano copper oxide, has complicated preparation process and high cost, and only has good adsorption and lifting effects on the heavy metal arsenic.
Patent CN 111620532A describes a Na type 2 CO 3 The modified fly ash adsorbs heavy metals in the sludge pyrolysis process, but the pyrolysis temperature is higher and is higher than 800 ℃, and Na above 800 ℃ is mainly utilized 2 CO 3 Decomposing to change the pore structure of the fly ash, but Na is used at medium and low temperature (400-600 ℃) 2 CO 3 Does not decompose and is therefore unsuitable.
Patent CN 111735056B describes a technology for capturing heavy metals in garbage incinerator by using percolate modified kaolin, which uses Na in the percolate + The characteristic of melting at high temperature promotes the adsorption of heavy metals on the surface of kaolin at high temperature, and the technology has the same requirement on the temperature of the incinerator and is not suitable for the enrichment of heavy metals in the incinerator at medium and low temperatures.
The methods have certain effects on the in-furnace enrichment effect of heavy metals in the solid waste heat treatment process, but at present, the methods still have several problems, namely the methods are firstly used as an additive which is not recovered in the furnace, and the preparation method is too complicated or the modified materials are too expensive, so that the cost is too high; secondly, in the prior art, the implementation cases are mostly aimed at single heavy metals, and the research on the cooperative control effect of multiple heavy metals is less; finally, the prior art aims at more heavy metal control additives in a furnace in a high-temperature environment of more than 800 ℃ of garbage incineration, researches on the anoxic pyrolysis environment at 400-600 ℃ are less, different pyrolysis environments can cause different existence forms of heavy metals in the pyrolysis process, and the mechanism of heavy metal adsorption by the additives in the high-temperature aerobic environment is not suitable for the medium-low-temperature anoxic environment, which are all the problems to be solved urgently in the research and development technology of the additives in the furnace for controlling the heavy metals in the current garbage pyrolysis process.
The kaolin is used as a common silicon-aluminum-based ore adsorbent, has the advantages of low cost and easy obtainment, and has relatively good effect of enriching heavy metals in the silicon-aluminum-based additive, but the natural kaolin has limited effect of adsorbing the heavy metals, and the synergistic adsorption effect on various heavy metals is still to be improved; meanwhile, at present, the kaolin has a certain research on enrichment of heavy metals in a furnace for coal combustion or household garbage combustion in a high-temperature oxygen-enriched environment, but the existing modification aims at improving the adsorption capacity of the kaolin on heavy metal oxides in the oxygen-enriched combustion process, and has little relation on heavy metal chlorides mainly existing in the low-temperature pyrolysis process.
The phosphate is widely applied to the heavy metal removal of soil and water, and particularly has good adsorption effect on heavy metal lead. And compared with silicate, the heavy metal phosphate precipitate is easier to form, and the same amount of phosphate anions can be combined with more heavy metal ions, so that the adsorption capacity of the adsorbent is improved, and a good foundation is laid for developing a new adsorbent. Although phosphate-based heavy metal trapping properties have been widely reported in solution, there is little control of heavy metals in furnaces used in the pyrolysis of waste.
In summary, in-furnace additives for adsorbing heavy metals in the low-temperature pyrolysis process of household garbage are yet to be developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a heavy metal adsorbent in a solid-waste pyrolysis process and a preparation and use method thereof, wherein the heavy metal adsorbent is based on cheap natural mineral kaolin, phosphate is assisted to modify, a modified additive and garbage are mixed and burned together, and heavy metals can diffuse to the surface of the additive with a pore structure in the pyrolysis process and react to generate substances such as aluminosilicate, phosphate and the like which are not easy to volatilize, so that migration of the heavy metals to flue gas is effectively reduced, and harm of the heavy metals to downstream tail gas treatment facilities is reduced.
The aim of the invention is realized by the following technical scheme:
the heavy metal adsorbent comprises phosphate and aluminosilicate/aluminosilicate minerals, wherein the impregnation ratio of the phosphate to the aluminosilicate/aluminosilicate minerals is 2.5% -30%, and the mass concentration of the phosphate is 4.17-50 g/L.
In the invention, the impregnation ratio is the mass ratio of the aluminosilicate mineral to the solute in the impregnation liquid.
The phosphate is one of sodium dihydrogen phosphate, sodium dihydrogen phosphate and sodium phosphate.
Further, the silica-alumina-based/aluminosilicate minerals are kaolin, montmorillonite, bentonite, igneous rock and feldspar, and the kaolin comprises kaolinite, mullite and quartz.
The invention also provides a preparation method of the heavy metal adsorbent, which comprises the following steps:
s1, preparing phosphate impregnation liquid;
s2, adding the impregnating solution and the silicon-aluminum base/silicon-aluminum mineral into a stirrer, wherein the temperature range is 60-90 ℃, the stirring speed is 500-1500 r/min, and the impregnating time is 4-12 h;
and S3, fully stirring, performing centrifugal filtration, wherein the centrifugal rotation speed is 2500-3500 r/min, the centrifugal time is 10-20 min, drying, calcining and grinding the composite additive obtained after filtration to obtain the heavy metal adsorbent, and drying at the temperature of 95-105 ℃ for 12-24 h.
Further, the heavy metal adsorbent in the step S3 is sieved by a 100-mesh sieve.
The third aspect of the invention provides a use method of the heavy metal adsorbent, wherein the heavy metal adsorbent is mixed with garbage and then sent into a pyrolysis furnace, the pyrolysis environment in the pyrolysis furnace is anaerobic or anoxic, and the pyrolysis temperature of the pyrolysis furnace is 400-600 ℃.
Specifically, nitrogen or carbon dioxide is introduced into the pyrolysis furnace to maintain an anaerobic or anoxic environment.
Preferably, the mixing mass ratio of the heavy metal adsorbent to the garbage is 1% -6%.
The reaction mechanism of the invention is as follows:
when the heavy metal adsorbent is prepared by adopting the impregnation method, sodium phosphate, sodium pyrophosphate and sodium metaphosphate and heavy metal molecules CrCl 3 、CdCl 2 、PbCl 2 、As 4 The reactivity of the (C) is greater than that of the aluminosilicate mineral, so that the phosphate modifying property improves the adsorption capacity of the additive to heavy metal molecules; meanwhile, sodium metaphosphate is gradually melted at 500-600 ℃, so that the transfer of heavy metal molecules adsorbed on the surface of the heavy metal adsorbent to the inside of the silicon aluminum base/silicon aluminum mineral can be promoted, adsorption sites on the surface of the silicon aluminum base/silicon aluminum mineral are vacated, and the reaction probability of heavy metal of the silicon aluminum base/silicon aluminum mineral is increased.
The beneficial effects of the invention are as follows:
1. in terms of cost, the kaolin is cheap and easy to obtain as natural minerals, the phosphate modification cost is lower than that of pure phosphate, meanwhile, the phosphate modification can obviously improve the enrichment advantage of the kaolin on various heavy metals, and the modification method used by the invention is an impregnation method, so that the method is simple and easy to operate compared with other modification methods, is convenient for large-scale preparation, and can be widely applied to engineering practice.
2. Compared with the traditional method of spraying active carbon before a bag-type dust collector to control heavy metals, the method reduces the cost of controlling heavy metals compared with active carbon on one hand, and controls heavy metals in pyrolysis residues on the other hand, so that heavy metals in flue gas are effectively reduced, harm of heavy metals to flue gas treatment facilities is reduced, such as denitration catalyst poisoning is caused, dioxin generation is catalyzed, the heavy metal content in desulfurized gypsum is too high, and quality of desulfurized gypsum is affected.
3. The thermodynamic calculation shows that the existence form of heavy metals under the condition of household garbage pyrolysis is more chloride, and whether experiments or quantum chemical calculation show that the addition of phosphate can obviously improve the adsorption of kaolin to heavy metal chloride in the household garbage pyrolysis process, make up for the short plates of kaolin on the adsorption of heavy metal chloride, and meanwhile, in terms of the potential ecological risk of pyrolysis residues after the addition of the additive, the addition of the kaolin phosphate composite additive can increase the generation of residual heavy metals compared with the pure phosphate for capturing heavy metals, thereby being beneficial to the stabilization of pyrolysis residues.
Drawings
FIG. 1 is a flow chart for the preparation of heavy metal adsorbents;
FIG. 2 is an XRD pattern of sodium monohydrogen phosphate modified kaolin, sodium dihydrogen phosphate modified kaolin, sodium phosphate modified kaolin, and kaolin;
FIG. 3 is a diagram of an experimental device for controlling heavy metal content in a household garbage pyrolysis process by a heavy metal adsorbent;
FIG. 4 shows retention of heavy metal Cr, cd, pb, as with the addition of kaolin and various heavy metal adsorbents without heavy metal adsorbents at a pyrolysis temperature of 500 ℃;
FIG. 5 shows the retention rate of heavy metal Cr, cd, pb, as in the pure garbage at the pyrolysis temperature of 400-600 ℃;
FIG. 6 shows retention of heavy metal Cr, cd, pb, as in pure kaolin at a pyrolysis temperature of 400-600 ℃;
FIG. 7 shows the retention rate of heavy metal Cr, cd, pb, as at a pyrolysis temperature of 400-600 ℃ with a mass ratio of kaolin to sodium dihydrogen phosphate of 5%;
FIG. 8 shows retention of sodium dihydrogen phosphate at 500℃pyrolysis temperature with different impregnation ratios to heavy metal Cr, cd, pb, as;
FIG. 9 shows retention rates of various added proportions of heavy metal Cr, cd, pb, as of heavy metal adsorbents prepared by adding sodium dihydrogen phosphate modified kaolin at a pyrolysis temperature of 500 ℃;
1-a nitrogen cylinder; 2-a flow meter; 3-pyrolysis device; 4-a cooling device; 5-tail gas treatment device.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without any inventive effort, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
Example 1:
s1, weighing 5g of sodium dihydrogen phosphate, and adding 150mL of ultrapure water to prepare an impregnating solution with the mass concentration of 33.3 g/L;
s2, adding 5g of kaolin and 30ml of the impregnating solution prepared in the step S1 into a constant-temperature water bath stirrer, wherein the impregnating ratio is 20%, the water bath temperature is 60 ℃, the stirring rotating speed is 1500 r/min, and the impregnating time is 4 hours;
s3, fully stirring, centrifugally filtering, wherein the centrifugal speed is 2700 r/min, the centrifugal time is 15min, drying, calcining, grinding and screening the composite additive obtained after filtering, drying for 12h under the drying condition of 105 ℃, and screening by a 100-mesh sieve to obtain the heavy metal adsorbent (HP-Kaolin).
Example 2:
s1, weighing 5g of sodium dihydrogen phosphate, and adding 150mL of ultrapure water to prepare an impregnating solution with the mass concentration of 33.3 g/L;
s2, adding 5g of kaolin and 30ml of the impregnating solution prepared in the step S1 into a constant-temperature water bath stirrer, wherein the impregnating ratio is 20%, the water bath temperature is 70 ℃, the stirring rotating speed is 800 r/min, and the impregnating time is 10h;
s3, fully stirring, centrifugally filtering, wherein the centrifugal speed is 3500 r/min, the centrifugal time is 20min, drying, calcining, grinding and screening the composite additive obtained after filtering, drying for 20H under the drying condition of 95 ℃, and screening by a 100-mesh sieve to obtain the heavy metal adsorbent (H2P-Kaolin).
Example 3:
s1, weighing 5g of sodium phosphate, and adding 150mL of ultrapure water to prepare an impregnating solution with the mass concentration of 33.3 g/L;
s2, adding 5g of kaolin and 30mL of the impregnating solution prepared in the step S1 into a constant-temperature water bath stirrer, wherein the impregnating ratio is 20%, the water bath temperature is 90 ℃, the stirring rotating speed is 500 r/min, and the impregnating time is 12h;
s3, fully stirring, centrifugally filtering, wherein the centrifugal speed is 2500 r/min, the centrifugal time is 10min, drying, calcining, grinding and screening the composite additive obtained after filtering, drying for 24h under the drying condition of 100 ℃, and screening by a 100-mesh sieve to obtain the heavy metal adsorbent (HP-Kaolin).
Example 4:
weighing garbage 5g, mixing with 0.25g of the heavy metal adsorbent prepared in example 1, putting into a stainless steel tube of a tube furnace, introducing nitrogen, setting the flow of the introduced nitrogen to be 2L/min, checking the air tightness of the device, and heating to 500 ℃ for 1h. After pyrolysis is completed, nitrogen is continuously introduced to cool to room temperature, the sample is taken out, dried, sealed and stored, and the experiment is repeated for three times under the same working condition. Digestion of heavy metals in pyrolytic carbon is carried out in a graphite digestion instrument, 0.1g pyrolytic carbon is weighed in a digestion tank, and HNO is sequentially added 3 、HClO 4 The amounts of HF are 8mL, 2mL and 2mL, the digestion temperature is 120 ℃, the contents of the digested heavy metals Cr, cd and Pb are tested by adopting atomic absorption, and the heavy metals As are tested by adopting ICP-AES.
Example 5:
in this example, unlike example 4, waste 5g was weighed and mixed with 0.25g of the heavy metal adsorbent prepared in example 2, and placed in a tube furnace.
Example 6:
in this example, sludge 5g was weighed and mixed with the heavy metal adsorbent prepared in example 3 of 0.25. 0.25g in a tube furnace, differently from example 4.
Example 7:
s1, weighing 1g of sodium dihydrogen phosphate, and adding 120mL of ultrapure water to prepare an impregnating solution with the mass concentration of 8.33 g/L;
s2, adding 5g of kaolin and 30ml of the impregnating solution prepared in the step S1 into a constant-temperature water bath stirrer, wherein the impregnating ratio is 5%, the water bath temperature is 60 ℃, the stirring rotating speed is 1200 r/min, and the impregnating time is 4 hours;
s3, fully stirring, centrifugally filtering, wherein the centrifugal speed is 3000 r/min, the centrifugal time is 20min, drying, calcining, grinding and screening the composite additive obtained after filtering, drying for 24h under the drying condition of 105 ℃, and screening by a 100-mesh sieve to obtain the heavy metal adsorbent.
Example 8:
a comparative experiment was conducted as in example 4 with 5g of pure waste, 5g of waste and 0.25g of kaolin mixture, and 5g of waste and 0.25g of heavy metal adsorbent mixture prepared in example 7, at a temperature of 400-600 ℃.
Example 9:
unlike example 7, 2g of sodium dihydrogen phosphate was weighed and 120mL of ultrapure water was added thereto, the mass concentration of the impregnation liquid was 16.67g/L, and the impregnation ratio was 10%.
Example 10:
unlike example 7, 0.5g of sodium dihydrogen phosphate was weighed and 120mL of ultrapure water was added thereto, the mass concentration of the impregnation liquid was 4.17g/L, and the impregnation ratio was 2.5%.
Example 11:
unlike example 7, 6g of sodium dihydrogen phosphate was weighed and 120mL of ultrapure water was added thereto, the mass concentration of the immersion liquid was 50g/L, and the immersion ratio was 30%.
Example 12:
in this example, 5g of garbage was weighed and mixed with 0.25g of the additives of examples 2, 7, 9 to 11, and added to a tube furnace, and an experiment was performed as in example 4.
Example 13:
in this example, 5g of refuse was weighed and mixed with 0.05g, 0.1g, 0.15g, 0.2g and 0.25g,0.3g of the additive of example 7, respectively, and tested as in example 4.
Conclusion:
as can be seen from the experimental results of examples 4-6, the heavy metal adsorbent obtained by phosphate modification of Kaolin has a lifting effect on enriching four heavy metals, wherein the H2P-Kaolin has the best effect; as can be seen from the experimental results of example 8, as the temperature increases, the retention rate of the four heavy metals gradually decreases, and the kaolin has an effect of improving the four heavy metals, and compared with pure kaolin, the sodium dihydrogen phosphate modified kaolin has a more obvious effect of improving. From the experimental results of example 12, it can be seen that the retention rates of the four heavy metals all showed a tendency to rise and then fall with increasing impregnation ratio. From the experimental results of example 13, it can be seen that the increase of the addition ratio can improve the contact opportunity of the additive and the heavy metals, and the enrichment effect of the four heavy metals is enhanced along with the increase of the addition ratio.
The foregoing is merely a preferred embodiment of the invention, and it is to be understood that the invention is not limited to the form disclosed herein but is not to be construed as excluding other embodiments, but is capable of numerous other combinations, modifications and environments and is capable of modifications within the scope of the inventive concept, either as taught or as a matter of routine skill or knowledge in the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (9)
1. A heavy metal adsorbent in a solid-waste pyrolysis process is characterized in that: the heavy metal adsorbent comprises phosphate and aluminosilicate/aluminosilicate minerals, wherein the impregnation ratio of the phosphate to the aluminosilicate/aluminosilicate minerals is 2.5% -30%, and the mass concentration of the phosphate is 4.17-50 g/L.
2. The heavy metal adsorbent according to claim 1, characterized in that: the phosphate is one of sodium dihydrogen phosphate, sodium dihydrogen phosphate and sodium phosphate.
3. The heavy metal adsorbent according to claim 1, characterized in that: the silicon-aluminum-based/silicon-aluminum mineral is kaolin, montmorillonite, bentonite, igneous rock or feldspar.
4. A heavy metal adsorbent according to claim 3, characterized in that: the kaolin comprises kaolinite, mullite and quartz.
5. The method for preparing the heavy metal adsorbent according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:
s1, preparing phosphate impregnation liquid;
s2, adding the impregnating solution and the silicon-aluminum base/silicon-aluminum mineral into a stirrer, wherein the temperature range is 60-90 ℃, the stirring speed is 500-1500 r/min, and the impregnating time is 4-12 h;
and S3, fully stirring, performing centrifugal filtration, wherein the centrifugal rotation speed is 2500-3500 r/min, the centrifugal time is 10-20 min, drying, calcining and grinding the composite additive obtained after filtration to obtain the heavy metal adsorbent, and drying at the temperature of 95-105 ℃ for 12-24 h.
6. The method for producing heavy metal adsorption according to claim 5, wherein: and S3, sieving the heavy metal adsorbent by adopting a 100-mesh sieve.
7. The method for using heavy metal adsorption according to any one of claims 1 to 4, wherein: and mixing the heavy metal adsorbent with garbage, and then delivering the mixture into a pyrolysis furnace, wherein the pyrolysis environment in the pyrolysis furnace is anaerobic or anoxic, and the pyrolysis temperature of the pyrolysis furnace is 400-600 ℃.
8. The method of using the heavy metal adsorbent according to claim 7, characterized in that: and introducing nitrogen or carbon dioxide into the pyrolysis furnace.
9. The method of using the heavy metal adsorbent according to claim 7, characterized in that: the mixing mass ratio of the heavy metal adsorbent to the garbage is 1% -6%.
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