CN112756376A - Synchronous calcium fixation dechlorination water washing method for waste incineration fly ash - Google Patents
Synchronous calcium fixation dechlorination water washing method for waste incineration fly ash Download PDFInfo
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- CN112756376A CN112756376A CN202011597742.9A CN202011597742A CN112756376A CN 112756376 A CN112756376 A CN 112756376A CN 202011597742 A CN202011597742 A CN 202011597742A CN 112756376 A CN112756376 A CN 112756376A
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- fly ash
- calcium
- waste incineration
- dechlorination
- fixing
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- 239000010881 fly ash Substances 0.000 title claims abstract description 167
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 80
- 239000011575 calcium Substances 0.000 title claims abstract description 80
- 238000004056 waste incineration Methods 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000005406 washing Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 47
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 53
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 30
- 239000000654 additive Substances 0.000 claims description 27
- 230000000996 additive effect Effects 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 24
- 239000001488 sodium phosphate Substances 0.000 claims description 22
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 22
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 22
- 239000004115 Sodium Silicate Substances 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 16
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 abstract description 51
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 49
- 229910052801 chlorine Inorganic materials 0.000 abstract description 49
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 48
- 239000002699 waste material Substances 0.000 abstract description 33
- 238000002386 leaching Methods 0.000 abstract description 24
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 230000008569 process Effects 0.000 description 26
- 230000009467 reduction Effects 0.000 description 23
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 18
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 18
- 238000007711 solidification Methods 0.000 description 18
- 230000008023 solidification Effects 0.000 description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 16
- 229910052918 calcium silicate Inorganic materials 0.000 description 16
- 239000000378 calcium silicate Substances 0.000 description 16
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 15
- 229910052793 cadmium Inorganic materials 0.000 description 15
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 15
- 229910052804 chromium Inorganic materials 0.000 description 15
- 239000011651 chromium Substances 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 239000011133 lead Substances 0.000 description 14
- 238000010828 elution Methods 0.000 description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000003795 desorption Methods 0.000 description 6
- 239000011505 plaster Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 230000002308 calcification Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002994 raw material 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000004127 vitreous body Anatomy 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a synchronous calcium fixation dechlorination water washing method for waste incineration fly ash. The method is a new idea of washing the waste incineration fly ash, can realize the efficient dechlorination of the waste incineration fly ash and can obviously reduce the concentration of heavy metal and calcium ions in the fly ash washing liquid, thereby reducing the treatment pressure of the downstream fly ash washing liquid. The method can remove more than 96% of chlorine in the waste incineration fly ash to the maximum extent, can retain more than 98% of calcium in the washed calcium-fixing dechlorination fly ash to the maximum extent, and can reduce more than 99% of heavy metal leaching in the washing waste liquid to the maximum extent.
Description
Technical Field
The invention relates to a synchronous calcium fixation dechlorination water washing method for waste incineration fly ash, belonging to the field of harmless treatment and resource utilization of hazardous wastes.
Background
The waste incineration fly ash refers to a particulate matter generated by condensation or chemical reaction of substances such as heavy metals, inorganic salts and the like volatilized under a high temperature condition in a waste incineration process. Fly ash from waste incineration is still listed in catalog of hazardous waste (2021 edition) at present. The waste incineration fly ash not only contains heavy metal and dioxin pollutants, but also contains 5 to 25 percent of chlorine. Typically, the content of chlorine in the grate fly ash is significantly higher than in the fluidized bed fly ash. Currently, the most main resource products of the waste incineration fly ash comprise three types, namely cement, vitreous body and ceramsite. However, the chlorine content of cement, glass body and ceramsite is very strict, for example, according to the related cement quality standard, the chlorine content in cement can not exceed 0.06%, and for example, according to the related light aggregate quality standard, the chlorine content in sintered or sintered ceramsite can not exceed 0.02%. Meanwhile, if the fly ash is not subjected to dechlorination pretreatment in the process of firing cement, glass bodies and ceramsite by utilizing the waste incineration fly ash, a large amount of chlorine in the fly ash is easily converted into atmosphere in the firing process, so that the waste gas treatment cost is increased, and the corrosion of a furnace body is accelerated.
Therefore, before the fly ash is subjected to resource conversion, dechlorination pretreatment is carried out on the fly ash. At present, a water washing method is one of the most common methods for dechlorinating waste incineration fly ash. Although the water washing method can realize effective dechlorination of the waste incineration fly ash, the water washing method also has a plurality of defects. For example, the fly ash washing process generates a large amount of washing waste liquid, which belongs to secondary dangerous waste and contains a large amount of salt, calcium, chlorine, heavy metals and dioxin pollutants. The process of treating the water washing waste liquid comprises the steps of decalcification, filtration and evaporative crystallization. However, the existing washing waste liquid has low decalcification efficiency, so that the calcium impurity content in the waste salt generated by evaporative crystallization is high. Meanwhile, the heavy metals contained in the crystallized waste salt are difficult to separate, so that the further treatment and utilization of the waste salt are limited.
Therefore, if a novel water washing method can be developed, the key for solving the current water washing bottleneck is to reduce the migration of calcium and heavy metals from fly ash particles to a water body in the water washing process on the premise of ensuring effective dechlorination.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a synchronous calcium fixation dechlorination water washing method for waste incineration fly ash.
The technical scheme is as follows: the invention relates to a synchronous calcium fixation dechlorination water washing method for waste incineration fly ash, which comprises the following steps:
(1) mixing sodium phosphate and sodium silicate to obtain a phosphorus-silicon additive;
(2) mixing the phosphorus-silicon additive with the waste incineration fly ash to obtain silicon-doped phosphorus fly ash;
(3) adding water into the silicon-phosphorus doped fly ash, mixing, continuously stirring, standing and aging to obtain calcium-fixing fly ash slurry;
(4) carrying out solid-liquid separation on the calcium-fixing fly ash slurry to obtain solid part which is calcium-fixing fly ash;
(5) mixing water and calcium-fixing fly ash mud, and continuously stirring to obtain calcium-fixing dechlorination fly ash mortar;
(6) and (3) carrying out solid-liquid separation on the calcium-fixing dechlorination flying mortar to obtain a solid part, namely the calcium-fixing dechlorination flying mortar.
In the step (1), the molar ratio of the sodium phosphate to the sodium silicate is 1-4: 10.
In the step (2), the mass ratio of the phosphorus-silicon additive to the waste incineration fly ash is 2-20: 100.
In the step (3), the solid-to-solid ratio of the water to the silicon-phosphorus-doped fly ash liquid is 0.3-0.9: 1, the continuous stirring time is 1-6 hours, and the standing and aging time is 12-48 hours.
Wherein, in the step (4) and the step (6), one of a plate filter press and a centrifuge is used for the solid-liquid separation.
In the step (5), the liquid-solid ratio of the water to the calcium-fixing fly ash is 1-3: 1, and the continuous stirring time is 1-6 h.
The reaction mechanism is as follows: in the invention, after water and fly ash doped with silicon and phosphorus are mixed, sodium phosphate, sodium silicate and alkali salt in the fly ash are quickly dissolved in the stirring process. During aging, the phosphate dissolved in the slurry reacts with the calcium oxide and calcium carbonate in the fly ash to form hydroxyapatite, while the silicate reacts with the calcium oxide and calcium carbonate in the fly ash to form calcium silicate. Calcium in fly ash slurry achieves effective fixation through the formation of hydroxyapatite and calcium silicate. Meanwhile, the hydroxyapatite and the calcium silicate can transfer heavy metal ions dissolved in the water body to the solid phase again through ion exchange and electrostatic adsorption. Under the alkali excitation action, calcium silicate and hydroxyapatite can further react to generate calcium silicophosphate, so that heavy metal and calcium in fly ash can be further stabilized. The calcium-fixing fly ash slurry is led into a plate filter press or a centrifuge for solid-liquid separation to remove free chloride ions. The water and the calcium fixation fly ash mud are mixed, and the chloride ions adsorbed on the surface of the calcium fixation fly ash mud can be promoted to be resolved into a water body in the stirring process, so that the fly ash can be synchronously fixed with calcium and heavy metals, and dechlorination can be maximized.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the method can realize the efficient dechlorination of the waste incineration fly ash and can obviously reduce the concentration of heavy metal and calcium ions in the fly ash water washing liquid, thereby reducing the treatment pressure of the downstream fly ash water washing waste liquid, and the method is a new idea for the waste incineration fly ash water washing. The method can realize the removal of more than 96 percent of chlorine in the waste incineration fly ash to the maximum extent; the highest calcium retention rate can be realized, more than 98 percent of calcium is retained in the water-washed calcium-fixing dechlorination fly ash; the leaching of more than 99 percent of heavy metal in the washing waste liquid is reduced to the maximum.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings
The household garbage incineration fly ash is taken from a certain normally-cooked garbage incineration power plant and collected by a bag-type dust collector. The waste incineration fly ash sample mainly contains 30-45% of CaO, 10-20% of Cl and 6-12% of Na2O、6％～12％K2O、3％～8％SO2、3％～8％SiO2、2％～6％MgO、2％～6％Fe2O3、2％～6％Al2O3、0.5％～1.5％CrO30.1 to 0.5 percent of CdO, 0.1 to 0.5 percent of NiO, 0.1 to 0.5 percent of PbO and the like.
Example 1 the effect of sodium phosphate and sodium silicate molar ratio on fly ash calcium solidification rate, percent reduction in heavy metal leaching, chlorine elution rate
The treatment process of the invention comprises the following steps: and respectively weighing sodium phosphate and sodium silicate according to the molar ratio of the sodium phosphate to the sodium silicate of 0.5:10, 0.7:10, 0.9:10, 1:10, 2.5:10, 4:10, 4.5:10, 5:10 and 6:10, and mixing to obtain the nine groups of phosphorus-silicon additives. And weighing the phosphorus-silicon additive and the waste incineration fly ash respectively according to the mass ratio of 2:100 of the phosphorus-silicon additive to the waste incineration fly ash, and mixing to obtain nine groups of silicon-doped phosphorus fly ash. And respectively weighing water and the silicon-phosphorus doped fly ash according to the liquid-solid ratio of 0.3:1, mixing, continuously stirring for 1h, standing and aging for 12h to obtain nine groups of calcium fixation fly ash. And (3) introducing the calcium-fixed fly ash slurry into a plate-type filter press for solid-liquid separation to obtain solid part calcium-fixed fly ash. And (3) weighing water and calcium-fixing fly ash according to the liquid-solid ratio of 1:1, mixing, and continuously stirring for 1h to obtain nine groups of calcium-fixing dechlorination fly ash. And (3) introducing the nine groups of calcium-fixing dechlorination fly ash slurry into a plate type filter press for solid-liquid separation to obtain solid calcium-fixing dechlorination fly ash, wherein the solid part is water washing waste liquid, and the total of the nine groups are respectively nine.
And (3) contrast treatment process: and (3) weighing water and the waste incineration fly ash according to the liquid-solid ratio of 1.3:1, mixing, and continuously stirring for 1h to obtain fly ash slurry. And (3) introducing the fly ash slurry into a plate-type filter press for solid-liquid separation to obtain dechlorinated fly ash as a solid part and washing waste liquid as a liquid part.
Determination of the calcium content in the solid sample: the calcium content of the waste incineration fly ash raw sample and the calcium-fixing dechlorination fly ash is measured according to the content measurement of calcium, magnesium and sulfur in the compound fertilizer (GB T19203-2003).
Calculation of calcium cure rate: the calcium retention rate of the waste incineration fly ash is calculated according to the formula (1), JCaIs calcium solidification rate, wherein cCa0And cCatThe calcium contents (%) of the raw waste incineration fly ash and the calcium-fixing dechlorinated fly ash are respectively.
Determination of the chlorine content in the solid sample: the chlorine content in the waste incineration fly ash raw sample and the calcium-fixing dechlorination fly ash is measured according to the construction sand (GB/T14684-.
Calculation of chlorine elution rate: the chlorine removal rate of the waste incineration fly ash is calculated according to the formula (2), RClFor chlorine removal efficiency, wherein cCl0And cCltThe chlorine contents (%) of the waste incineration fly ash raw sample and the calcium fixation dechlorinated fly ash are respectively.
And (3) determining the concentrations of chromium, nickel, lead and cadmium in the liquid: the concentrations of the nickel, lead and cadmium in the water washing waste liquid obtained in the treatment process and the comparative treatment process are measured according to an inductively coupled plasma emission spectrometry (HJ 776-2012015) for measuring 32 elements in water quality, and the concentration of the chromium pollutant is measured according to a flow injection-dibenzocarbonyl dihydrazide photometry (HJ 908-2017) for measuring hexavalent chromium in water quality.
The percentage reduction of leaching of chromium, nickel, lead and cadmium is calculated as follows: the percent reduction in leaching of chromium, nickel, lead and cadmium is calculated according to equation (3), where RMReducing the leaching percentage of chromium, nickel, lead and cadmium (M is chromium, nickel, lead and cadmium), cM0Concentrations of chromium, nickel, lead, cadmium (mg/L) in the aqueous waste for comparative treatment, and cMtThe concentrations (mg/L) of chromium, nickel, lead and cadmium in the water washing waste liquid in the treatment process of the invention are shown.
The test results of this example are shown in tables 1 and 2.
TABLE 1 table of calcium content and chlorine content in fly ash as raw material, heavy metal concentration in washing waste liquid in comparative treatment process, and calcification content and chlorine content in calcium fixation dechlorination fly ash and heavy metal concentration in washing waste liquid under the influence of different molar ratios of sodium phosphate and sodium silicate in treatment process of the invention
Table 2 table of the effect of sodium phosphate and sodium silicate molar ratio on fly ash calcium solidification rate, percentage reduction in heavy metal leaching, and chlorine elution rate
As can be seen from Table 1, the calcium content of the fly ash is 27.15%, the chlorine content is 18.34%, and the concentrations of chromium, nickel, lead and cadmium in the washing waste liquid in the comparative treatment process are 978.24mg/L, 345.13mg/L, 267.45mg/L and 131.62mg/L, respectively. Meanwhile, the content of calcium in the calcium-fixing dechlorination flying plaster, the content of chlorine in the calcium-fixing dechlorination flying plaster and the concentration of heavy metals in the water washing waste liquid obtained by contrasting the treatment process are all influenced by the change of the molar ratio of the sodium phosphate to the sodium silicate. Specifically, as can be seen from the analysis in table 2, when the molar ratio of sodium phosphate to sodium silicate is less than 1:10, the amount of sodium phosphate is less, the amount of generated hydroxyapatite is reduced, so that the amount of heavy metal ions adsorbed by ion exchange in the hydroxyapatite is reduced, resulting in a significant reduction in the percentage of reduction in leaching of heavy metals as the molar ratio of sodium phosphate to sodium silicate is reduced. When the molar ratio of the sodium phosphate to the sodium silicate is 1-4: 10, hydroxyapatite can be formed by the phosphate and calcium oxide and calcium carbonate in the fly ash in the aging process, and calcium silicate is formed by the silicate and calcium oxide and calcium carbonate in the fly ash. Both hydroxyapatite and calcium silicate can adsorb and stabilize calcium and heavy metals dissolved from fly ash into water. Meanwhile, under the alkali excitation action, calcium silicate and hydroxyapatite can further react to generate a calcium silicophosphate substance, so that the heavy metal and calcium in the fly ash can be further stabilized. Finally, the calcium solidification rate is greater than 94%, the chlorine desorption rate is greater than 92%, and the heavy metal leaching reduction percentage is greater than 92%. When the molar ratio of the sodium phosphate to the sodium silicate is more than 4:10, the generated hydroxyapatite is excessive, the ion exchange property of calcium, chlorine and heavy metal is enhanced, and the reduction percentages of the calcium solidification rate, the chlorine desorption rate and the heavy metal leaching are all obviously reduced along with the further increase of the molar ratio of the sodium phosphate to the sodium silicate. Therefore, the benefit and the cost are combined, and when the molar ratio of the sodium phosphate to the sodium silicate is 1-4: 10, the fly ash calcium solidification rate, the heavy metal leaching reduction percentage and the chlorine elution rate are improved.
Example 2 the quality ratio of fly ash calcium solidification rate, heavy metal leaching reduction percentage, chlorine elution rate influence of phosphorus silicon additive and waste incineration fly ash
And respectively weighing sodium phosphate and sodium silicate according to the molar ratio of 4:10 of the sodium phosphate to the sodium silicate, and mixing to obtain the phosphorus-silicon additive. And respectively weighing the phosphorus-silicon additive and the waste incineration fly ash according to the mass ratio of the phosphorus-silicon additive to the waste incineration fly ash of 1:100, 1.5:100, 1.8:100, 2:100, 11:100, 20:100, 21:100, 23:100 and 25:100, and mixing to obtain nine groups of silicon-doped phosphorus fly ash. And (3) respectively weighing water and the silicon-phosphorus doped fly ash according to the liquid-solid ratio of 0.6:1, mixing, continuously stirring for 3.5 hours, standing and aging for 30 hours to obtain nine groups of calcium fixation fly ash. And (3) introducing the nine groups of calcium-fixing fly ash slurry into a centrifuge for solid-liquid separation to obtain nine groups of calcium-fixing fly ash slurry as solid parts. Weighing water and calcium fixation fly ash according to the liquid-solid ratio of 2:1, mixing, and continuously stirring for 3.5h to obtain nine groups of calcium fixation dechlorination fly ash. And (3) introducing the nine groups of calcium-fixing dechlorination fly ash slurry into a centrifugal machine for solid-liquid separation to obtain solid calcium-fixing dechlorination fly ash, wherein the solid part is water washing waste liquid, and the total of the nine groups are respectively nine.
And (3) contrast treatment process: and (3) weighing water and the waste incineration fly ash according to the liquid-solid ratio of 2.6:1, mixing, and continuously stirring for 1h to obtain fly ash slurry. And (3) introducing the fly ash slurry into a plate-type filter press for solid-liquid separation to obtain dechlorinated fly ash as a solid part and washing waste liquid as a liquid part.
The measurement of calcium content, the measurement of chlorine content, the measurement of chromium, nickel, lead and cadmium concentrations in the washing waste liquid, the calculation of chlorine elution rate, the calculation of calcium solidification rate and the calculation of the leaching reduction percentage of heavy metals of chromium, nickel, lead and cadmium are the same as those in example 1, and the specific results are shown in tables 3 and 4.
TABLE 3 table of calcium content and chlorine content in fly ash raw sample, heavy metal concentration in washing waste liquid in comparative treatment process, and calcification content and chlorine content in calcium fixation dechlorination fly ash and heavy metal concentration in washing waste liquid under the influence of different mass ratios of phosphorus silicon additive and waste incineration fly ash in treatment process of the invention
TABLE 4 influence of the mass ratio of phosphorus-silicon additive to fly ash from incineration on the solidification rate of calcium in fly ash, the percentage reduction of heavy metal leaching, and the chlorine elution rate
As can be seen from Table 3, the calcium content of the fly ash was 28.54%, the chlorine content was 19.02%, and the concentrations of chromium, nickel, lead and cadmium in the washing waste liquid in the comparative treatment process were 824.76mg/L, 297.42mg/L, 221.68mg/L and 145.19mg/L, respectively. Meanwhile, the content of calcium in the calcium-fixing dechlorination flying plaster, the content of chlorine in the calcium-fixing dechlorination flying plaster and the concentration of heavy metals in the washing waste liquid obtained in the contrast treatment process are all influenced by the change of the mass ratio of the phosphorus-silicon additive to the waste incineration fly ash. Specific influence conditions can be analyzed from table 4, and when the mass ratio of the phosphorus silicon additive to the waste incineration fly ash is less than 2:10, the mixing amount of the phosphorus silicon additive is less, and the generation amounts of hydroxyapatite, calcium silicate and calcium silicophosphate substances are reduced, so that the calcium solidification rate, the reduction percentage of heavy metal leaching and the chlorine elution rate are all obviously reduced along with the reduction of the mass ratio of the phosphorus silicon additive to the waste incineration fly ash. When the mass ratio of the phosphorus-silicon additive to the waste incineration fly ash is 2-20: 10, in the aging process, calcium oxide and calcium carbonate in phosphate and fly ash can form hydroxyapatite, and calcium silicate and calcium oxide and calcium carbonate in fly ash form calcium silicate. Both hydroxyapatite and calcium silicate can adsorb and stabilize calcium and heavy metals dissolved from fly ash into water. Meanwhile, under the alkali excitation action, calcium silicate and hydroxyapatite can further react to generate a calcium silicophosphate substance, so that the heavy metal and calcium in the fly ash can be further stabilized. Finally, the calcium solidification rate is greater than 94%, the chlorine desorption rate is greater than 94%, and the heavy metal leaching reduction percentage is greater than 96%. When the mass ratio of the phosphorus-silicon additive to the waste incineration fly ash is more than 20:10, the calcium solidification rate, the chlorine desorption rate and the heavy metal leaching reduction percentage are not obviously changed along with the further increase of the mass ratio of the phosphorus-silicon additive to the waste incineration fly ash. Therefore, the benefit and the cost are combined, and when the mass ratio of the phosphorus-silicon additive to the waste incineration fly ash is 2-20: 10, the fly ash calcium solidification rate, the heavy metal leaching reduction percentage and the chlorine desorption rate are improved most beneficially.
Example 3 Effect of aging time on fly ash calcium solidification Rate, percent reduction in heavy metal leaching, chlorine elution Rate
And respectively weighing sodium phosphate and sodium silicate according to the molar ratio of 4:10 of the sodium phosphate to the sodium silicate, and mixing to obtain the phosphorus-silicon additive. And respectively weighing the phosphorus-silicon additive and the waste incineration fly ash according to the mass ratio of 20:100 of the phosphorus-silicon additive to the waste incineration fly ash, and mixing to obtain the silicon-doped phosphorus fly ash. Respectively weighing water and the silicon-doped phosphorus fly ash according to the liquid-solid ratio of 0.9:1, mixing, continuously stirring for 6h, and respectively standing and aging for 6h, 8h, 10h, 12h, 30h, 48h, 54h, 60h and 66h to obtain the calcium-fixing fly ash slurry. And (3) introducing the calcium-fixing fly ash slurry into a centrifugal machine for solid-liquid separation to obtain solid part which is calcium-fixing fly ash. Respectively weighing water and calcium-fixing fly ash according to the liquid-solid ratio of 3:1, mixing, and continuously stirring for 6h to obtain calcium-fixing dechlorination fly ash. Introducing the calcium-fixed dechlorination flying mortar into a plate-type filter press for solid-liquid separation to obtain nine groups of solid parts from the calcium-fixed dechlorination flying mortar and liquid parts from the washing waste liquid.
And (3) contrast treatment process: and (3) weighing water and the waste incineration fly ash according to the liquid-solid ratio of 3.9:1, mixing, and continuously stirring for 1h to obtain fly ash slurry. And (3) introducing the fly ash slurry into a plate-type filter press for solid-liquid separation to obtain dechlorinated fly ash as a solid part and washing waste liquid as a liquid part.
The measurement of calcium content, the measurement of chlorine content, the measurement of chromium, nickel, lead and cadmium concentrations in the washing waste liquid, the calculation of chlorine elution rate, the calculation of calcium solidification rate and the calculation of the leaching reduction percentage of heavy metals of chromium, nickel, lead and cadmium are the same as those in example 1, and the specific results are shown in tables 5 and 6.
TABLE 5 tables of calcium content and chlorine content of fly ash as raw material, heavy metal concentration in washing waste liquid in comparative treatment process, and calcification content and chlorine content in calcium fixation dechlorination fly ash and heavy metal concentration in washing waste liquid under the influence of aging time in treatment process of the present invention
TABLE 6 influence of aging time on fly ash calcium solidification rate, heavy metal leaching reduction percentage, chlorine elution rate
As can be seen from Table 5, the calcium content of the fly ash was 28.17%, the chlorine content was 18.78%, and the concentrations of chromium, nickel, lead and cadmium in the washing waste liquid in the comparative treatment process were 889.52mg/L, 311.05mg/L, 219.31mg/L and 128.79mg/L, respectively. Meanwhile, the content of calcium in the calcium-fixing dechlorination flying plaster, the content of chlorine in the calcium-fixing dechlorination flying plaster and the concentration of heavy metals in the washing waste liquid obtained in the contrast treatment process are all influenced by the change of the mass ratio of the phosphorus-silicon additive to the waste incineration fly ash. Specifically, as can be seen from the analysis in table 6, when the aging time is less than 12h, the aging time of the mortar is too short, and the formation of hydroxyapatite and calcium silicate is reduced, so that the calcium curing rate and the percentage reduction of leaching of heavy metals are both significantly reduced with the decrease of the aging time. When the aging time is 12-48 h, in the aging process, the phosphate and calcium oxide and calcium carbonate in the fly ash can form hydroxyapatite, and the silicate and calcium oxide and calcium carbonate in the fly ash form calcium silicate. Both hydroxyapatite and calcium silicate can adsorb and stabilize calcium and heavy metals dissolved from fly ash into water. Meanwhile, under the alkali excitation action, calcium silicate and hydroxyapatite can further react to generate a calcium silicophosphate substance, so that the heavy metal and calcium in the fly ash can be further stabilized. Finally, the calcium solidification rate is greater than 95%, the chlorine desorption rate is greater than 95%, and the heavy metal leaching reduction percentage is greater than 97%. When the aging time is more than 48 hours, excessive chlorine is adsorbed into the silico-calcium phosphate substance, resulting in a significant decrease in the chlorine elution rate with further increase in the aging time. Therefore, the benefit and the cost are combined, and when the aging time is equal to 12-48 h, the fly ash calcium solidification rate, the heavy metal leaching reduction percentage and the chlorine elution rate are improved.
Claims (6)
1. A synchronous calcium fixation dechlorination water washing method for waste incineration fly ash is characterized by comprising the following steps:
(1) mixing sodium phosphate and sodium silicate to obtain a phosphorus-silicon additive;
(2) mixing the phosphorus-silicon additive with the waste incineration fly ash to obtain silicon-doped phosphorus fly ash;
(3) adding water into the silicon-phosphorus doped fly ash, mixing, continuously stirring, standing and aging to obtain calcium-fixing fly ash slurry;
(4) carrying out solid-liquid separation on the calcium-fixing fly ash slurry to obtain solid part which is calcium-fixing fly ash;
(5) mixing water and calcium-fixing fly ash mud, and continuously stirring to obtain calcium-fixing dechlorination fly ash mortar;
(6) and (3) carrying out solid-liquid separation on the calcium-fixing dechlorination flying mortar to obtain a solid part, namely the calcium-fixing dechlorination flying mortar.
2. The synchronous calcium fixation dechlorination water washing method for the waste incineration fly ash according to claim 1, wherein in the step (1), the molar ratio of the sodium phosphate to the sodium silicate is 1-4: 10.
3. The synchronous calcium fixation dechlorination water washing method for the waste incineration fly ash according to claim 1, wherein in the step (2), the mass ratio of the phosphorus-silicon additive to the waste incineration fly ash is 2-20: 100.
4. The synchronous calcium fixation dechlorination water washing method for the waste incineration fly ash according to claim 1, wherein in the step (3), the liquid-solid ratio of the water to the silicon-doped phosphorus fly ash is 0.3-0.9: 1, the continuous stirring time is 1-6 hours, and the standing and aging time is 12-48 hours.
5. The synchronous calcium fixation dechlorination water washing method for the waste incineration fly ash according to claim 1, wherein in the step (4) and the step (6), the solid-liquid separation uses one of a plate filter press or a centrifuge.
6. The synchronous calcium fixation dechlorination water washing method for the waste incineration fly ash according to claim 1, wherein in the step (5), the liquid-solid ratio of the water to the calcium fixation fly ash is 1-3: 1, and the continuous stirring time is 1-6 h.
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