CN115141002A - Method for fixing chlorine in household garbage incineration fly ash - Google Patents
Method for fixing chlorine in household garbage incineration fly ash Download PDFInfo
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- CN115141002A CN115141002A CN202210646663.5A CN202210646663A CN115141002A CN 115141002 A CN115141002 A CN 115141002A CN 202210646663 A CN202210646663 A CN 202210646663A CN 115141002 A CN115141002 A CN 115141002A
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- Prior art keywords
- fly ash
- chlorine
- mixture
- household garbage
- fixing
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- 239000000460 chlorine Substances 0.000 title claims abstract description 75
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 72
- 239000010881 fly ash Substances 0.000 title claims abstract description 71
- 239000010813 municipal solid waste Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 238000002309 gasification Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 23
- 230000000382 dechlorinating effect Effects 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 22
- 229940069978 calcium supplement Drugs 0.000 claims abstract description 21
- 239000004034 viscosity adjusting agent Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 11
- 238000009837 dry grinding Methods 0.000 claims abstract description 9
- 238000001238 wet grinding Methods 0.000 claims abstract description 9
- 239000003623 enhancer Substances 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 37
- 239000002956 ash Substances 0.000 claims description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 20
- 239000002893 slag Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000011324 bead Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000010008 shearing Methods 0.000 claims description 12
- 239000010440 gypsum Substances 0.000 claims description 11
- 229910052602 gypsum Inorganic materials 0.000 claims description 11
- 239000012744 reinforcing agent Substances 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000009628 steelmaking Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 238000004043 dyeing Methods 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000010802 sludge Substances 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000011863 silicon-based powder Substances 0.000 claims description 4
- 230000009919 sequestration Effects 0.000 claims 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 18
- 238000002386 leaching Methods 0.000 abstract description 17
- 239000002920 hazardous waste Substances 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000004566 building material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000005406 washing Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 239000010791 domestic waste Substances 0.000 description 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 150000001804 chlorine Chemical class 0.000 description 3
- 239000010883 coal ash Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000126 substance Substances 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
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/1328—Waste materials; Refuse; Residues without additional clay
-
- 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
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
-
- 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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- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/027—Lightweight materials
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/448—Sulphates or sulphites
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- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract
The invention discloses a method for fixing chlorine in fly ash generated by burning household garbage, which comprises the steps of carrying out wet grinding on a chlorine fixing agent, a gasification dechlorinating agent and a calcium supplement in a ball mill, and drying to obtain a mixture A; then dry grinding the dried domestic garbage incineration fly ash and the mixture A to obtain a mixture B; then adding a viscosity modifier, a surface friction modifier and a toughness enhancer into the mixture B, and uniformly mixing to obtain a mixture C; then carrying out extrusion forming on the mixture C to obtain a forming body; then controlling the temperature and humidity to make the liquid in the formed body run off at a proper speed and the green body shrinks slowly; and pre-calcining the green body with stable and unchangeable space dimension at 300-500 ℃ and then calcining at 900-1100 ℃ to obtain a sintered product. The invention realizes the fixation of chlorine in the fly ash, so that the proportion of dissolved chlorine in the stabilized fly ash is less than one thousandth, the leaching of heavy metals in the sintered product is lower than the toxic leaching limit of the identification standard of hazardous wastes, and the sintered product has certain hardness and can be used as a building material.
Description
Technical Field
The invention relates to the technical field of environmental engineering, in particular to a method for fixing chlorine in fly ash generated by burning household garbage.
Background
The incineration of the household garbage is a main mode for treating the household garbage due to harmlessness, good recycling effect and remarkable volume and weight reduction effects, but a large amount of fly ash generated from the incineration of the household garbage is classified as dangerous waste due to high content of heavy metals, chlorine and dioxin. At present, a great deal of research work is carried out on the treatment of heavy metals and dioxin, but the treatment mode of chlorine salt is poor. The presence of large amounts of chloride salts can cause the fly ash to contaminate the soil and environment during landfilling, as well as cause equipment plugging and cement kiln wall corrosion during cement kiln co-processing. In the process of harmless and resource utilization of fly ash, chloride can also influence the strength of cement and aggregate, and the corrosion speed of reinforced concrete is accelerated. Therefore, the chlorine salt in the fly ash is treated before the fly ash is reused.
The current common chlorine salt treatment mode is water washing, but water washing only can remove soluble chlorine in fly ash, and the existence of high chlorine leads to high cost of water washing water, more importantly, a large amount of high-concentration inorganic salt wastewater needing to be treated can be generated at the same time, and the wastewater can be discharged up to the standard and needs additional technology to be treated. This method is not only costly but also, but also harmful to the environment. According to the technical specification of fly ash pollution control of household garbage incineration (HJ 1134-2020), the content of soluble chlorine is less than 2%, preferably not more than 1% in the manner that fly ash treatment products are used for producing other utilization modes except cement clinker. This criterion may not be met by water washing alone.
For water-insoluble chlorine, the common treatment methods are acid washing, alkali washing and high-temperature calcination. The acid washing and alkali washing are to convert water-insoluble chloride into water-soluble chloride and dissolve the water-soluble chloride in water, and the high-temperature calcination is to volatilize or decompose the chloride at high temperature. Acid washing and alkali washing need to consume a large amount of acid and alkali, and waste liquid is generated, high-temperature calcination can volatilize a large amount of heavy metal chloride salt, and further secondary fly ash with larger pollution is formed.
The fly ash contains calcium up to 40-60%, and the calcium-containing compound mainly comprises CaClOH and CaCO 3 、CaSO 4 、Ca(OH) 2 And the like. The water soluble chlorine in the fly ash mainly comprises CaClOH, naCl, KCl and the like, and accounts for 59-93% of the total chlorine. The CaClOH is also the main reason that the fly ash is strongly alkaline.
The aluminum ash is solid waste generated in the process of melting aluminum, such as aluminum electrolysis, aluminum alloy production, aluminum scrap regeneration and the like. The aluminum ash can be divided into primary aluminum ash and secondary aluminum ash. The primary aluminum ash is mainly used in electrolysis aluminum or cast aluminum. The secondary aluminum ash is generated in the remelting primary aluminum ash or aluminum alloy refining process. The salts, chlorides and fluorides in the aluminum ash corrode recovery equipment, the aluminum ash is easy to deliquesce and generate malodorous gases such as ammonia gas and methane after being accumulated for a long time, and the excessive suction can cause discomfort and even poisoning of human bodies. Aluminum ash was officially listed in the national records of hazardous waste in 2016 due to its reactivity and toxicity.
CaO-SiO 2 -Al 2 O 3 Systems are commonly found in fly ash disposal processes. The current treatment of chlorine is usually to remove it, and how to fix it is a new direction of research.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a method for fixing chlorine in fly ash generated by burning household garbage, which changes the existing method for treating chlorine in fly ash and develops a new way to fix chlorine in fly ash generated by burning household garbage. The proportion of dissolved chlorine in the stabilized fly ash is not more than 1 per thousand, the leaching of heavy metal in the sintered product is lower than the toxic leaching limit of the identification standard of hazardous waste, and the sintered product has certain hardness, can be used as a building material, and meets the requirements of waste recycling and environmental protection.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a method for fixing chlorine in fly ash generated by burning household garbage comprises the following steps:
(1) Wet-grinding a chlorine fixing agent, a gasification dechlorinating agent and a calcium supplement in a ball mill, and drying to obtain a mixture A;
(2) Dry-grinding the dried domestic garbage incineration fly ash and the mixture A in a ball mill to obtain a mixture B;
(3) Adding a viscosity regulator, a surface friction regulator and a toughness reinforcing agent into the mixture B, and uniformly mixing to obtain a mixture C;
(4) Placing the mixture C in a hydraulic forming machine, extruding through a strip-shaped cylindrical die, and changing the shearing rate along with the change of the shearing stress to obtain a formed body;
(5) Controlling the temperature and humidity to make the liquid in the formed body run off and separate out, and slowly shrinking the volume of the formed body to obtain a green body;
(6) Calcining the green body with stable and unchangeable space dimension, pre-calcining at 300-500 ℃, and then calcining at 1000-1100 ℃ to obtain a sintered product.
Preferably, in the step (1), the chlorine fixing agent is aluminum ash, and the aluminum ash contains at least one of primary aluminum ash and secondary aluminum ash.
Preferably, in the step (1), the gasification dechlorinating agent is at least one of steel-making slag, coal slag, silica fume and fly ash.
Preferably, in the step (1), the calcium supplement is at least one of carbide slag, printing and dyeing sludge, medical gypsum and desulfurized gypsum.
Preferably, in the step (1), the mass percent of the aluminum oxide in the chlorine fixing agent is 40-60wt.%, the mass percent of the silicon dioxide in the gasification dechlorinating agent is 30-50wt.%, and the mass percent of the calcium oxide in the calcium supplement agent is 30-60wt.%.
Preferably, in the step (1), the mass ratio of the chlorine fixing agent to the gasification dechlorination agent to the calcium supplement is (1.7-2.6): (1.2-2.0): (1.0-1.8).
Preferably, in the step (1), the wet grinding is performed by using absolute ethyl alcohol as a ball milling medium, the diameter of ball milling beads is 3.5-10mm, and the ball-to-material ratio is 5:1-10:1, ball milling for 2-4h in a planetary ball mill with the rotating speed of 250-400 r/min.
Preferably, in the step (1), the drying temperature is 100-105 ℃, and the drying time is 18-24h.
Preferably, in the step (2), the fly ash from the incineration of the household garbage refers to a trapped substance in a flue gas purification system and a dust removal device in the incineration process of the household garbage.
Preferably, in the step (2), the fly ash contains 20-30wt.% of chlorine and 40-60wt.% of calcium, wherein the mass percent of the CaClOH accounts for 10-15wt.% of the fly ash.
Preferably, in the step (2), the mass ratio of the fly ash to the mixture a is (1.5-2.0): 1.
preferably, in the step (2), the dry milling means that the fly ash and the mixture A are ball milled for 4 to 6 hours in a planetary ball mill with the rotating speed of 250 to 400r/min, the ball milling bead diameter is 5 to 12mm, and the ball-to-material ratio is 7:1-10:1.
preferably, in the step (3), the viscosity modifier comprises an organic viscosity modifier and an inorganic viscosity modifier, wherein the organic viscosity modifier is at least one of sodium carboxymethyl cellulose, methyl cellulose and polyvinyl alcohol, and the inorganic viscosity modifier is at least one of silica sol, aluminum phosphate and clay.
Preferably, in the step (3), the surface friction modifier is glycerol.
Preferably, in the step (3), the toughness enhancer is at least one of glass fiber, silica gel, and pseudoboehmite.
Preferably, in the step (3), the mass percentages of the viscosity modifier, the surface friction modifier and the toughness enhancer in the mixture B are respectively 1-3wt.%, 0.5-2.5wt.% and 3.5-5wt.%.
Preferably, in the step (4), the diameter of the die in the shape of a bar-shaped cylinder is phi =4 to 5mm, and the horizontal inclination angle at the time of extrusion by the hydroforming machine is 30 to 90 °.
Preferably, in the step (5), the controlling of the temperature and the humidity means that the molded body is placed at room temperature, naturally dried for 24-48h under the air humidity of 40-80%, and then placed in an oven to be dried for 18-24h at the temperature of not lower than 105 ℃.
Preferably, in the step (6), the dimensional stability of the space is that the diameter and height of the green body are not changed any more.
Preferably, in the step (6), the pre-calcination time is 1-2h, and the high-temperature calcination time is 2-4h.
Preferably, in the step (6), the soluble chlorine content of the sintered product is not higher than 0.12wt.%, and further preferably, the soluble chlorine content of the sintered product is 0.03-0.12wt.%.
The principle of the invention is as follows:
the strong alkalinity in the fly ash from the incineration of household garbage comes from the decomposition of CaClOH which is unstable in water and is easily decomposed into Ca (OH) 2 And CaCl 2 But has good thermal stability.
In CaO-SiO 2 -Al 2 O 3 Under the system, caClOH and SiO 2 Dechlorination reaction is carried out by SiCl 4 Form (b) volatilizes, siO 2 Favour the gasification of Cl, but Al 2 O 3 The presence of SiO inhibits 2 The gasification of Cl results in the presence of Cl in the solid phase in mineral form. As shown in the following chemical equation:
the invention realizes the fixation of chlorine in the fly ash, so that the proportion of dissolved chlorine in the stabilized fly ash is less than one thousandth, and the leaching of heavy metals in the sintered product is lower than the toxic leaching limit of the identification standard of hazardous wastes.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the chlorine in the fly ash is fixed in the mineral after sintering, so that the proportion of the dissolved chlorine in the stabilized fly ash is less than one thousandth, and the requirements of technical Specification for controlling pollution of the fly ash from incineration of household garbage (HJ 1134-2020) are met;
2. the leaching concentration of the heavy metal of the sintered product is lower than the limit value of the concentration of the heavy metal in the control standard of domestic waste landfill (GB 16889-2008);
3. the strength of the sintered product is determined according to the lightweight aggregate and the lightweight aggregate of part 1 of the test method (GB-T17431.1-2010) of the lightweight aggregate, and the national requirements on high-strength lightweight aggregate of buildings are met;
4. the method realizes the chlorine fixation of the fly ash generated by burning the household garbage, realizes the reclamation and the reutilization of wastes, saves production and living resources, and has great significance for environmental protection.
Detailed Description
In the following embodiments, the fly ash from incineration of domestic garbage refers to the trapped matter in the flue gas purification system and the dust removal device during the incineration of domestic garbage; the fly ash contains 20-30wt.% of chlorine and 40-60wt.% of calcium, wherein the content of CaClOH in percentage by mass accounts for 10-15wt.% of the fly ash.
In the following embodiments, the chlorine fixing agent is aluminum ash, and the aluminum ash comprises at least one of primary aluminum ash and secondary aluminum ash; the gasification dechlorinating agent is at least one of steel-making slag, coal slag, micro silicon powder and coal ash; the calcium supplement is at least one of carbide slag, printing and dyeing sludge, medical gypsum and desulfurized gypsum.
In the following embodiments, the viscosity modifier includes an organic viscosity modifier and an inorganic viscosity modifier, wherein the organic viscosity modifier is at least one of sodium carboxymethylcellulose, methylcellulose and polyvinyl alcohol, and the inorganic viscosity modifier is at least one of silica sol, aluminum phosphate and clay; the surface friction modifier is glycerol; the toughness reinforcing agent is at least one of glass fiber, silica gel and pseudoboehmite.
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1
In this embodiment, a method for fixing chlorine in fly ash generated by burning household garbage includes the following steps:
(1) Chlorine fixing agent, gasification dechlorinating agent and calcium supplement agent are mixed according to the mass ratio of 1.8:1.5:1.3; absolute ethyl alcohol is used as a ball milling medium, the diameter of ball milling beads is 3.5mm, and the ball-material ratio is 5:1, wet grinding for 2 hours in a planetary ball mill with the rotating speed of 250r/min, and then drying for 18 hours at 100 ℃ to obtain a mixture A;
the content of aluminum oxide in the chlorine fixing agent is 56.7wt.%, the content of silicon dioxide in the gasification dechlorinating agent is 40.0wt.%, and the content of calcium oxide in the calcium supplement is 43.1wt.%; the chlorine fixing agent is secondary aluminum ash; the gasification dechlorinating agent is steel-making slag and coal ash (mass ratio is 1; the calcium supplement is composed of carbide slag and printing and dyeing sludge (mass ratio is 2;
(2) Mixing the dry domestic garbage incineration fly ash with the mixture A according to the mass ratio of 1.5:1, the diameter of ball milling beads is 5mm, and the ball-material ratio is 7:1, carrying out dry grinding for 4 hours in a ball mill with the rotating speed of 300r/min to obtain a mixture B;
(3) Adding 1wt.% of viscosity regulator, 0.5wt.% of surface friction regulator and 3.5wt.% of toughness reinforcing agent into the mixture B by mass percent and uniformly mixing to obtain a mixture C; the viscosity regulator comprises an organic viscosity regulator and an inorganic viscosity regulator, wherein the organic viscosity regulator is sodium carboxymethylcellulose, and the inorganic viscosity regulator is silica sol; the surface friction modifier is glycerol; the toughness reinforcing agent is glass fiber;
(4) Placing the mixture C in a hydraulic forming machine, and extruding through a strip-shaped cylindrical die, wherein the diameter phi of the die is =4mm, the horizontal inclination angle during extrusion is 30 degrees, and the shearing rate is changed along with the change of shearing stress, so that a formed body with good extrudability is obtained;
(5) Controlling the temperature and humidity, naturally drying the formed body for 24 hours at room temperature under the air humidity of 40%, and then drying the formed body for 18 hours in a drying oven at 105 ℃ to slowly shrink the green body;
(6) Pre-calcining the green body with stable and unchangeable space dimension at 300 ℃ for 1h, and then calcining at 1000 ℃ for 2h to obtain a sintered product.
Experimental test analysis:
according to the mass percentage, the sintered product of the embodiment is detected, the soluble chlorine content is 0.03wt.%, the heavy metal leaching amount is lower than the heavy metal leaching limit in the control standard of domestic waste landfill (GB 16889-2008), the cylinder pressure strength is 12.24MPa, and the density is 730kg/m 3 The water absorption rate is 5.67 percent, and the national building high-strength light aggregate requirement is met.
Example 2
This embodiment is substantially the same as embodiment 1, and is characterized in that:
in this embodiment, a method for fixing chlorine in fly ash generated by burning household garbage includes the following steps:
(1) Chlorine fixing agent, gasification dechlorinating agent and calcium supplement agent are mixed according to the mass ratio of 2.0:1.6:1.5; absolute ethyl alcohol is used as a ball milling medium, the diameter of ball milling beads is 5mm, and the ball material ratio is 5:1, wet-milling in a planetary ball mill at the rotating speed of 300r/min for 2.5h, and then drying at 105 ℃ for 20h to obtain a mixture A;
the mass percent of aluminum oxide in the chlorine fixing agent is 51.0wt.%, the mass percent of silicon dioxide in the gasification dechlorinating agent is 37.5wt.%, and the mass percent of calcium oxide in the calcium supplement is 37.3wt.%; the chlorine fixing agent is primary aluminum ash and secondary aluminum ash (the mass ratio is 7; the gasification dechlorinating agent is coal cinder; the calcium supplement is medical gypsum and desulfurized gypsum (mass ratio is 5;
(2) Mixing the dry domestic garbage incineration fly ash with the mixture A according to the mass ratio of 1.6:1, the diameter of ball milling beads is 10mm, and the ball-material ratio is 7:1, dry-milling for 5 hours in a ball mill with the rotating speed of 250r/min to obtain a mixture B;
(3) Adding 1.5wt.% of viscosity regulator, 1.0wt.% of surface friction regulator and 3.5wt.% of toughness reinforcing agent into the mixture B, and uniformly mixing to obtain a mixture C; the viscosity regulator comprises an organic viscosity regulator and an inorganic viscosity regulator, wherein the organic viscosity regulator is methylcellulose, and the inorganic viscosity regulator is aluminum phosphate; the surface friction modifier is glycerol; the toughness enhancer is pseudoboehmite;
(4) Placing the mixture C in a hydraulic forming machine, and extruding through a strip-shaped cylindrical die, wherein the diameter phi of the die is =4mm, the horizontal inclination angle during extrusion is 45 degrees, and the shearing rate is changed along with the change of shearing stress, so that a formed body with good extrudability is obtained;
(5) Controlling the temperature and humidity, naturally drying the formed body for 24 hours at room temperature and 50% of air humidity, and then drying the formed body for 24 hours in a drying oven at 105 ℃ to slowly shrink the green body;
(6) Pre-calcining the green body with stable and unchangeable space dimension at 350 ℃ for 1h, and then calcining at 1000 ℃ for 3h to obtain a sintered product.
Experimental test analysis:
according to the mass percentage, the sintered product of the embodiment is detected, the soluble chlorine content is 0.06wt.%, the heavy metal leaching amount is lower than the heavy metal leaching limit in the control standard of domestic waste landfill (GB 16889-2008), the cylinder pressure strength is 11.63MPa, and the density is 759kg/m 3 The water absorption is 7.83 percent, and the national building high-strength lightweight aggregate requirement is met.
Example 3
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for fixing chlorine in fly ash generated by burning household garbage includes the following steps:
(1) Chlorine fixing agent, gasification dechlorinating agent and calcium supplement agent are mixed according to the mass ratio of 2.2:1.8:1.6; absolute ethyl alcohol is used as a ball milling medium, the diameter of ball milling beads is 5mm, and the ball material ratio is 7:1, wet grinding for 3h in a planetary ball mill with the rotating speed of 350r/min, and then drying for 24h at 105 ℃ to obtain a mixture A;
the mass percent of aluminum oxide in the chlorine fixing agent is 46.4wt.%, the mass percent of silicon dioxide in the gasification dechlorinating agent is 33.3wt.%, and the mass percent of calcium oxide in the calcium supplement is 35.0wt.%; the chlorine fixing agent is primary aluminum ash and secondary aluminum ash (the mass ratio is 5; the gasification dechlorinating agent is steel-making slag and micro silicon powder (the mass ratio is 7; the calcareous supplement is printing and dyeing sludge and carbide slag (mass ratio is 2;
(2) Mixing the dry domestic garbage incineration fly ash with the mixture A according to the mass ratio of 1.8:1, the diameter of ball milling beads is 10mm, and the ball-material ratio is 8:1, dry-milling for 5 hours in a ball mill with the rotating speed of 300r/min to obtain a mixture B;
(3) Adding 2.0wt.% of viscosity regulator, 1.5wt.% of surface friction regulator and 4.0wt.% of toughness enhancer into the mixture B, and uniformly mixing to obtain a mixture C; the viscosity regulator comprises an organic viscosity regulator and an inorganic viscosity regulator, wherein the organic viscosity regulator is polyvinyl alcohol, and the inorganic viscosity regulator is clay; the surface friction modifier is glycerol; the toughness reinforcing agent is silica gel;
(4) Placing the mixture C in a hydraulic forming machine, and extruding through a strip-shaped cylindrical die, wherein the diameter phi of the die is =5mm, the horizontal inclination angle during extrusion is 60 degrees, and the shearing rate is changed along with the change of shearing stress, so that a formed body with good extrudability is obtained;
(5) Controlling the temperature and humidity, naturally drying the formed body for 48h at room temperature and 60% of air humidity, and then drying the formed body for 24h in a drying oven at 105 ℃ to slowly shrink the green body;
(6) Pre-calcining the green body with stable and unchangeable space dimension at 400 ℃ for 1h, and then calcining at 1100 ℃ for 4h to obtain a sintered product.
Experimental test analysis:
according to the mass percentage, the sintered product of the embodiment is detected, the soluble chlorine content is 0.08wt.%, the heavy metal leaching amount is lower than the heavy metal leaching limit in the control standard of domestic waste landfill (GB 16889-2008), the cylinder pressure strength is 12.13MPa, and the density is 720kg/m 3 The water absorption rate is 6.43 percent, and the national requirement of building high-strength light aggregate is met.
Example 4
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for fixing chlorine in fly ash generated by burning household garbage includes the following steps:
(1) Chlorine fixing agent, gasification dechlorinating agent and calcium supplement agent are mixed according to the mass ratio of 2.5:2.0:1.8; absolute ethyl alcohol is used as a ball milling medium, the diameter of ball milling beads is 10mm, and the ball material ratio is 10:1, wet grinding for 4 hours in a planetary ball mill with the rotating speed of 400r/min, and then drying for 24 hours at 105 ℃ to obtain a mixture A;
the content of aluminum oxide in the chlorine fixing agent is 40.8wt.%, the content of silicon dioxide in the gasification dechlorinating agent is 30.0wt.%, and the content of calcium oxide in the calcium supplement is 31.1wt.%; the chlorine fixing agent is primary aluminum ash; the gasification dechlorinating agent is steel-making slag and coal ash (the mass ratio is 7; the calcium supplement is composed of carbide slag and desulfurized gypsum (the mass ratio is 3;
(2) Mixing the dry domestic garbage incineration fly ash with the mixture A according to the mass ratio of 2.0:1, the diameter of ball milling beads is 12mm, the ball material ratio is 10:1, dry-milling in a ball mill with the rotating speed of 400r/min for 6 hours to obtain a mixture B;
(3) Adding 2.5wt.% of viscosity regulator, 2.5wt.% of surface friction regulator and 4.5wt.% of toughness enhancer into the mixture B, and uniformly mixing to obtain a mixture C; the viscosity regulator comprises an organic viscosity regulator and an inorganic viscosity regulator, wherein the organic viscosity regulator is sodium carboxymethyl cellulose, and the inorganic viscosity regulator is clay; the surface friction modifier is glycerol; the toughness reinforcing agent is glass fiber;
(4) Placing the mixture C in a hydraulic forming machine, and extruding through a strip-shaped cylindrical die, wherein the diameter phi of the die is =5mm, the horizontal inclination angle during extrusion is 90 degrees, and the shearing rate is changed along with the change of shearing stress, so that a formed body with good extrudability is obtained;
(5) Controlling the temperature and humidity, naturally drying the formed body for 48h at room temperature and 80% of air humidity, and then drying the formed body for 24h in a drying oven at 105 ℃ to slowly shrink the green body;
(6) Pre-calcining the green body with stable and unchangeable space dimension at 500 ℃ for 2h, and then calcining at 1100 ℃ for 3h to obtain a sintered product.
Experimental test analysis:
according to the mass percentage, the sintered product obtained in the embodiment is detected, the soluble chlorine content is 0.12wt.%, the heavy metal leaching amount is lower than the heavy metal leaching limit in the control Standard for municipal solid waste landfill (GB 16889-2008), the cylinder pressure is 10.53MPa, and the density is 725kg/m 3 The water absorption rate is 8.42 percent, and the national requirement of building high-strength light aggregate is met.
Example 5
The present embodiment is substantially the same as the first embodiment, and the special points are that:
in this embodiment, the fly ash from incineration of household garbage refers to a collected substance in a flue gas purification system and a dust removal device during the incineration process of household garbage; the fly ash contains 20-30wt.% of chlorine and 40-60wt.% of calcium, wherein the content of CaClOH in percentage by mass accounts for 10-15wt.% of the fly ash.
In this embodiment, the chlorine fixing agent is aluminum ash, and the aluminum ash contains at least one of primary aluminum ash and secondary aluminum ash; the gasification dechlorinating agent is at least one of coal slag, micro silicon powder and fly ash, or further comprises steelmaking slag; the calcareous supplement is at least one of printing and dyeing sludge, medical gypsum and desulfurized gypsum, or also comprises carbide slag.
In the present embodiment, the viscosity modifier includes an organic viscosity modifier and an inorganic viscosity modifier; the organic viscosity regulator is at least one of methyl cellulose and polyvinyl alcohol, or also comprises sodium carboxymethyl cellulose; the inorganic viscosity regulator is at least one of aluminum phosphate and clay, or also contains silica sol; the surface friction modifier is glycerol; the toughness reinforcing agent is at least one of silica gel and pseudoboehmite, or also comprises glass fiber.
According to the mass percentage, the sintered product obtained by the embodiment is detected, the soluble chlorine content is not higher than 0.12wt.%, the heavy metal leaching amount is lower than the heavy metal leaching limit in the control Standard for municipal solid waste landfill (GB 16889-2008), the cylinder pressure strength is not higher than 12.24MPa, and the density is not higher than 759kg/m 3 The water absorption rate is not less than 5.67 percent, and the national building high-strength lightweight aggregate requirement is met。
While the embodiments of the present invention have been described, the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the invention should be made as equivalent substitutions without departing from the technical principle and inventive concept of the invention.
Claims (10)
1. A method for fixing chlorine by using fly ash generated by burning household garbage is characterized by comprising the following steps:
(1) Wet grinding a chlorine fixing agent, a gasification dechlorinating agent and a calcium supplement in a ball mill, and drying to obtain a mixture A;
(2) Dry-milling the dried domestic garbage incineration fly ash and the mixture A in a ball mill to obtain a mixture B;
(3) Adding a viscosity regulator, a surface friction regulator and a toughness reinforcing agent into the mixture B, and uniformly mixing to obtain a mixture C;
(4) Placing the mixture C in a hydraulic forming machine, extruding through a strip-shaped cylindrical die, and changing the shearing rate along with the change of the shearing stress to obtain a formed body;
(5) Controlling the temperature and humidity to make the liquid in the formed body run off and separate out, and slowly shrinking the volume of the formed body to obtain a green body;
(6) Calcining the green body with stable and unchangeable space dimension, pre-calcining at 300-500 ℃, and then calcining at 1000-1100 ℃ to obtain a sintered product.
2. The method for fixing chlorine by using fly ash generated by burning household garbage according to claim 1, which is characterized in that: in the step (1), the chlorine fixing agent is aluminum ash, and the aluminum ash comprises at least one of primary aluminum ash and secondary aluminum ash;
or, in the step (1), the gasification dechlorinating agent is at least one of steel-making slag, coal slag, micro silicon powder and fly ash;
or in the step (1), the calcium supplement is at least one of carbide slag, printing and dyeing sludge, medical gypsum and desulfurized gypsum.
3. The method for fixing chlorine by using fly ash generated by burning household garbage according to claim 1, which is characterized in that: in the step (1), the mass percent of the alumina in the chlorine fixing agent is 40-60wt.%, the mass percent of the silica in the gasification dechlorinating agent is 30-50wt.%, and the mass percent of the calcium oxide in the calcium supplement is 30-60wt.%;
or in the step (1), the mass ratio of the chlorine fixing agent to the gasification dechlorinating agent to the calcium supplement is (1.7-2.6): (1.2-2.0): (1.0-1.8).
4. The method for chlorine sequestration of fly ash from incineration of household garbage according to claim 1, wherein in the step (1), the wet milling is performed by using absolute ethyl alcohol as a ball milling medium, the diameter of ball milling beads is 3.5-10mm, and the ball-to-material ratio is 5:1-10:1, ball-milling for 2-4h in a planetary ball mill with the rotating speed of 250-400 r/min;
or, in the step (1), the drying temperature is 100-105 ℃, and the drying time is 18-24h.
5. The method for fixing chlorine in fly ash generated by burning domestic garbage according to claim 1, wherein in the step (2), the fly ash generated by burning domestic garbage refers to a captured matter in a flue gas purification system and a dust removal device in the process of burning domestic garbage;
or in the step (2), the fly ash contains 20-30wt.% of chlorine and 40-60wt.% of calcium, wherein the mass percent of CaClOH accounts for 10-15wt.% of the fly ash.
6. The method for chlorine sequestration of fly ash from incineration of household garbage according to claim 1, wherein in the step (2), the mass ratio of fly ash to the mixture A is (1.5-2.0): 1;
or, in the step (2), the dry milling means that the fly ash and the mixture A are ball-milled for 4-6h in a planetary ball mill with the rotating speed of 250-400r/min, the diameter of ball-milling beads is 5-12mm, and the ball-to-material ratio is 7:1-10:1.
7. the method for fixing chlorine in fly ash generated by incinerating household garbage according to claim 1, wherein in the step (3), the viscosity modifier comprises an organic viscosity modifier and an inorganic viscosity modifier, wherein the organic viscosity modifier is at least one of sodium carboxymethylcellulose, methylcellulose and polyvinyl alcohol, and the inorganic viscosity modifier is at least one of silica sol, aluminum phosphate and clay;
alternatively, in the step (3), the surface friction modifier is glycerol;
or, in the step (3), the toughness reinforcing agent is at least one of glass fiber, silica gel and pseudo-boehmite;
or in the step (3), the mass percentages of the viscosity modifier, the surface friction modifier and the toughness enhancer in the mixture B are respectively 1-3wt.%, 0.5-2.5wt.% and 3.5-5wt.%.
8. The method for chlorine sequestration of fly ash from incineration of household garbage according to claim 1, wherein in the step (4), the diameter of the cylindrical die in the shape of an extruded bar is phi = 4-5 mm, and the horizontal inclination angle of the hydraulic molding machine during extrusion is 30-90 °.
9. The method for fixing chlorine in fly ash generated in incineration of household garbage according to claim 1, wherein in the step (5), the controlling of the temperature and the humidity means that the molded body is placed at room temperature, naturally air-dried for 24-48h under the air humidity of 40-80%, and then placed in an oven to be dried for 18-24h at the temperature of not less than 105 ℃.
10. The method for chlorine sequestration of fly ash from incineration of household garbage according to claim 1, wherein in the step (6), the dimensional stability is unchanged, that is, the diameter and height of the green body are not changed;
or, in the step (6), the pre-calcination time is 1-2h, and the high-temperature calcination time is 2-4h.
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| CN117185691A (en) * | 2023-11-08 | 2023-12-08 | 浙江京兰低碳技术有限公司 | Method for regenerating baking-free artificial lightweight aggregate by cooperatively disposing aluminum ash and garbage incineration fly ash |
| CN117732831A (en) * | 2024-02-06 | 2024-03-22 | 华衍环保产业有限公司甘肃分公司 | Compatible additive for inhibiting volatilization of chloride salt in fly ash sintering process and fly ash treatment method |
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| CN117185691A (en) * | 2023-11-08 | 2023-12-08 | 浙江京兰低碳技术有限公司 | Method for regenerating baking-free artificial lightweight aggregate by cooperatively disposing aluminum ash and garbage incineration fly ash |
| CN117185691B (en) * | 2023-11-08 | 2024-01-19 | 浙江京兰低碳技术有限公司 | Method for regenerating baking-free artificial lightweight aggregate by cooperatively disposing aluminum ash and garbage incineration fly ash |
| CN117732831A (en) * | 2024-02-06 | 2024-03-22 | 华衍环保产业有限公司甘肃分公司 | Compatible additive for inhibiting volatilization of chloride salt in fly ash sintering process and fly ash treatment method |
| CN117732831B (en) * | 2024-02-06 | 2024-05-07 | 华衍环保产业有限公司甘肃分公司 | Compatible additive for inhibiting volatilization of chloride salt in fly ash sintering process and fly ash treatment method |
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