CN114956379A - Method for realizing fixation of arsenic in liquid by utilizing fly ash to form safe landfill - Google Patents
Method for realizing fixation of arsenic in liquid by utilizing fly ash to form safe landfill Download PDFInfo
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- CN114956379A CN114956379A CN202210599535.XA CN202210599535A CN114956379A CN 114956379 A CN114956379 A CN 114956379A CN 202210599535 A CN202210599535 A CN 202210599535A CN 114956379 A CN114956379 A CN 114956379A
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- fly ash
- arsenic
- liquid
- solid
- landfill
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 112
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000010881 fly ash Substances 0.000 title claims abstract description 87
- 239000007788 liquid Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000000694 effects Effects 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- 239000007787 solid Substances 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000009616 inductively coupled plasma Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002386 leaching Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 8
- 238000000295 emission spectrum Methods 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000009919 sequestration Effects 0.000 claims 8
- -1 arsenic ions Chemical class 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000010813 municipal solid waste Substances 0.000 description 26
- 229910052745 lead Inorganic materials 0.000 description 23
- 229910052804 chromium Inorganic materials 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 19
- 239000002351 wastewater Substances 0.000 description 18
- 239000010791 domestic waste Substances 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 238000004056 waste incineration Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OWTFKEBRIAXSMO-UHFFFAOYSA-N arsenite(3-) Chemical compound [O-][As]([O-])[O-] OWTFKEBRIAXSMO-UHFFFAOYSA-N 0.000 description 4
- 238000004993 emission spectroscopy Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000011278 co-treatment Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940000489 arsenate Drugs 0.000 description 2
- 229940103357 calcium arsenate Drugs 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 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 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/30—Landfill technologies aiming to mitigate methane emissions
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for fixing arsenic in liquid by utilizing fly ash to form a safe landfill, which takes fly ash as a raw material, has low price and belongs to waste recycling; the process is simple and easy to control, is not easily interfered by the outside, and has stable treatment effect; the fixation rate of arsenic ions in the liquid is nearly 100 percent; the obtained landfill has good stability and extremely low arsenic reverse dissolution rate.
Description
Technical Field
The invention belongs to the technical field of harmless treatment of hazardous wastes, and particularly relates to a method for fixing arsenic in liquid by utilizing fly ash to form a safe landfill.
Background
The household garbage incineration method has the advantages of small occupied area, high garbage weight and volume reduction ratio, high harmless level, flexible site selection, recoverable heat and the like, and the fly ash amount generated by household garbage incineration is also rapidly increased. The household garbage incineration fly ash is generated in a flue gas purification system of a household garbage incineration power plant, the generated amount is generally 3-5% of the household garbage, the household garbage incineration fly ash is white or light gray powder, the specific surface area is large, the porosity is high, and the household garbage incineration fly ash contains dioxin and various heavy metals and is generally classified as dangerous waste. At present, most of domestic garbage incineration fly ash is stabilized by adding a heavy metal stabilizer, and the heavy metal leaching toxicity reaches the standard and is buried.
Arsenic is a highly toxic substance, and arsenic-containing wastewater is produced in the production of related industrial enterprises. Common arsenic removal methods include adsorption, ion exchange, chemical precipitation, etc., wherein the more common methods are the following three methods:
the lime method mainly utilizes lime milk to react with arsenate ions or arsenite ions to generate insoluble calcium arsenate or calcium arsenite precipitates. The method can treat the wastewater with higher arsenic content, but the reaction speed is slow, and the fixation rate of the arsenic can only reach the comprehensive discharge standard of the sewage; and because of the high solubility of calcium arsenate and calcium arsenite, the arsenic-containing precipitate generated by water treatment can be reversely dissolved by rainwater and the like, thereby causing secondary pollution of arsenic.
The lime-iron salt method mainly utilizes lime milk and iron salt, utilizes arsenate and arsenite to form stable complex with iron and other metals, divalent iron ions are converted into trivalent iron ions under the condition of blowing air, and simultaneously trivalent arsenic ions are converted into pentavalent arsenic ions with toxicity smaller than that of trivalent arsenic ions, thereby FeAsO with very small solubility product is generated 4 Precipitation, conversion of calcium ions to Ca 3 (AsO 4 ) 2 And (4) precipitating. The precipitated arsenic-containing solid needs to be subjected to subsequent stabilization treatment and then to landfill.
Sulfide process, mainlyBy adding a vulcanizing agent, As is formed 2 S 3 And (4) precipitation, and a good arsenic removal effect is achieved. But As 2 S 3 The precipitate is stable only in acidic environment, and when the pH value is more than 1, As 2 S 3 Will be re-dissolved into the spent acid solution; therefore, the control of the addition amount of sulfide in the treatment process is very critical, and the arsenic oxide cannot be sufficiently removed due to insufficient addition amount of sulfide; excessive input amount can excessively consume hydrogen ions in the waste acid, so that the acidity is too low and even alkaline, and As is caused 2 S 3 The precipitate redissolved. Both of these conditions can severely degrade arsenic removal efficiency.
In a word, the existing arsenic treatment process in liquid has the problems of high process control requirement, easy influence and unstable effect in the removal process, or has the problem of secondary pollution caused by the fact that arsenic-containing precipitates are reversely dissolved under the action of rainwater and the like.
Disclosure of Invention
1. Problems to be solved
The invention provides a process aiming at the problems that the treatment process or process control requirement of arsenic in the existing liquid is high, the arsenic is easily influenced and the effect is unstable, or arsenic in arsenic-containing precipitates is easily dissolved back and causes secondary pollution.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
[1] a method for achieving arsenic fixation in a liquid to form a safe landfill using fly ash, comprising
1) Mixing fly ash with arsenic-containing liquid;
stirring;
standing;
2) separating to obtain solid landfill;
wherein,
1) adding the fly ash into the arsenic-containing liquid for N times, wherein N is more than or equal to 2;
1) the stirring time is 5-10 min, and the mixture after stirring is in a solid-liquid separation state;
1) in the method, the mixture obtained after the fly ash and the arsenic-containing liquid are mixed does not have fluidity in a standing state;
1) the standing time is 18-24 hours, and the mixture is in a state after the standing is finished. . . . . . . (ii) a
It is to be noted here that the above-mentioned,
as described in 1), mixing the fly ash with the arsenic-containing liquid N times in the process of mixing the fly ash with the arsenic-containing liquid is the key to ensure the stability of the finally obtained landfill, and the difficulty of arsenic dissolution:
the "gasification mode" as described in 2) means a mode of separating a liquid portion such as water contained in the mixture obtained in 1) from a solid portion, and is different from a conventional separation mode such as filtration, filter pressing, centrifugation, or the like. The "gasification mode" can be schematically that the mixture obtained in 1) is subjected to heat treatment such as drying, so that liquid is evaporated and gasified to be separated; alternatively, the "gasification mode" may be a mode in which the mixture obtained in 1) is treated with a gas flow having a certain velocity to take away a liquid part;
the 'gasification mode' is the key for ensuring that the arsenic ion fixation rate in the liquid is close to 100%.
[2] Further, 2), the separation process comprises
Heating at a certain temperature; or alternatively
Heating at a certain temperature, and condensing and recovering the evaporated liquid.
[3] Further, in 2), the heating temperature is 60 to 79 ℃, the heating state is generally kept for 18 to 24 hours, namely, the heating object can reach a constant weight state, and the treatment is finished, so that the solid landfill is obtained.
It should be noted that the heating temperature is 60-70 ℃, the boiler waste heat of the household garbage incineration power plant can be utilized in the actual operation, and the drying requirement can be met at the temperature.
[4] Further, in the step 1), the fly ash and the arsenic-containing liquid are mixed according to the solid-to-liquid ratio of 1.8-2.2 Kg to 1L;
in the step 1), the fly ash is added into the arsenic-containing liquid each time, and then the fly ash is stirred.
It should be noted that, according to the solid-liquid ratio, it can be ensured that the mixture obtained in 1) has no fluidity; under the condition, the fly ash needs to be added into the liquid for a plurality of times, and the fly ash needs to be stirred after being added into the arsenic-containing liquid every time;
the mixture prepared under the above conditions is one of the bases for ensuring the stability of the solid landfill finally obtained.
[5] Further, the fly ash has a particle size of not more than 200 μm, a bulk density of 0.5-1.0 g/cm, a water content of not more than 1.5%, and calcium hydroxide in an amount of not less than 30 wt%.
[6] Further, an arsenic-containing liquid, which contains arsenic in an amount of not more than 5000mg/L and has a pH of 5 to 8.
It should be noted that, on the basis of the above technical solutions [1] to [5], the pH of the arsenic-containing liquid itself is a key to ensure the stability of the finally obtained landfill, and the arsenic is not easily dissolved back: another key factor of the solid landfill with arsenic leaching amount below 1% when the solid landfill is leached with acetic acid solution with concentration of 0.1 mol/L.
[7] Further, the fly ash comprises metal elements and non-metal elements;
the metal elements comprise one or more of calcium, sodium, potassium, magnesium, zinc and aluminum;
the nonmetal elements comprise one or two of chlorine and silicon.
[8] Further, the fly ash is a product after pretreatment, and the pretreatment process comprises the following steps:
mixing fly ash with deionized water; the solid-liquid ratio of the mixture is not higher than 1kg to 20L;
oscillating; the oscillation time is 18-24 h, and the frequency is 120-;
carrying out centrifugal separation;
drying; the drying temperature was 105. + -. 2 ℃.
[9] Further, leaching the obtained solid landfill by using an acetic acid solution with the concentration of 0.1mol/L in a vibration treatment mode, and then taking the filtered supernatant to measure the content of arsenic contained in the supernatant by using inductively coupled plasma emission spectroscopy;
the arsenic leaching of the resulting solid landfill was calculated to be less than 1%.
[10] Further, the solid-liquid ratio of the acetic acid solution to the solid landfill is 1kg to 20L;
the room temperature of the leaching treatment is 25 +/-2 ℃.
[11] Furthermore, the arsenic-containing liquid can also contain heavy metals Pb, Cr and Cu;
and (3) leaching the solid landfill in the mode of [9], wherein the leaching amounts of Pb, Cr, Cu and the like of the obtained solid landfill are respectively lower than 5%, 3% and 1%.
3. Advantageous effects
Compared with the prior art, the method for fixing arsenic in liquid by utilizing fly ash to form safe landfill provided by the invention comprises the following steps:
the material is fly ash, the price is low, and the waste recycling is realized;
the process is simple and easy to control, is not easily interfered by the outside, and has stable treatment effect;
the fixation rate of arsenic ions in the liquid is nearly 100 percent;
the obtained landfill has good stability and extremely low arsenic reverse dissolution rate.
Drawings
FIG. 1 XRD pattern of fly ash used in example 1 of the present invention;
FIG. 2 is a result of measuring the amount of arsenic in the supernatant by inductively coupled plasma emission spectroscopy after the solid landfill obtained in example 1 of the present invention is leached by an acetic acid solution having a concentration of 0.1mol/L by means of oscillation treatment;
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise specified;
the essential features and the remarkable effects of the present invention can be obtained from the following examples, which are a part of the examples of the present invention, but not all of them, and therefore they do not limit the present invention in any way, and those skilled in the art will be able to make some insubstantial modifications and adaptations in view of the present invention, all falling within the scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; as used herein, the term and/or includes any and all combinations of one or more of the associated listed items.
Herein, the "constant weight" means a weight difference of the sample after two consecutive drying or ignition under given conditions of 0.3mg or less. The second and subsequent weighing, which was carried out to a constant weight, should be carried out after further drying for 1 hour under the specified conditions.
In the present context, the term "not lower than" or "not higher than" is intended to include the range, for example, "the amount of a substance is not lower than 100" is intended to mean "the amount of the substance may be 100 or higher than 100".
The invention is further described with reference to specific examples.
Example 1
The household garbage incineration fly ash is taken from a flue gas purification system of a household garbage incineration power plant, and has the particle size of not more than 200 mu m, the bulk density of about 0.8g/cm and the water content of not more than 1.5 percent;
the fly ash is pretreated by the following steps:
mixing fly ash with deionized water; the solid-liquid ratio of the mixture is not higher than 1kg to 20L;
oscillating; the oscillation time is 18h, and the frequency is 150 r/min;
carrying out centrifugal separation;
drying; the drying temperature was 105 ℃.
As shown in fig. 1, the main elements in the fly ash from incineration of household garbage were Ca 32.03 wt.%, Cl 27.46 wt.%, Na 11.17 wt.%, K6.00 wt.%, Si 0.95 wt.%, Mg 0.80 wt.%, Zn 0.41 wt.%, Al 0.30 wt.%, Pb 1260Mg/kg, Cr64Mg/kg, Cu351Mg/kg, As26Mg/kg, by X-ray fluorescence spectroscopy.
Firstly, 100g of domestic waste incineration fly ash is added into 100mL of deionized water to be mixed, and the mixture is stirred until solid and liquid are fully contacted;
then adding 100g of domestic waste incineration fly ash, stirring until solid and liquid are fully contacted, and continuing stirring for 5 min;
standing for 24h, drying the obtained mixture at 65 ℃ to constant weight to obtain a solid landfill, and condensing and recovering liquid during drying;
preparing an acetic acid solution with the concentration of 0.1mol/L, putting 20g of the obtained solid landfill into 400mL of the acetic acid solution, oscillating for 18h at 25 ℃, filtering the supernatant, measuring the contents of Pb, Cr, Cu and As by using an inductively coupled plasma emission spectrum, and calculating the fixed parts of the Pb, Cr, Cu and As to be 96.91%, 98.00%, 99.99% and 99.63% respectively As shown in figure 2. The result shows that the domestic waste incineration fly ash achieves the stabilizing effect.
Example 2
The properties of the fly ash from incineration of household garbage were the same as those of comparative example 1.
With Na 3 AsO 4 ·12H 2 And O, preparing simulated arsenic-containing wastewater with the arsenic concentration of 5000mg/L, wherein the pH is about 7 (the amplitude deviation is not more than 0.5).
Firstly, adding 100g of domestic waste incineration fly ash into 100mL of simulated arsenic-containing wastewater, mixing, and stirring until solid and liquid are fully contacted;
then adding 100g of domestic waste incineration fly ash, stirring until solid and liquid are fully contacted, and continuing stirring for 5 min;
standing for 24h, drying the obtained mixture at 65 ℃ for 220h to constant weight to obtain a solid landfill, and condensing and recovering liquid during drying;
preparing an acetic acid solution with the concentration of 0.1mol/L, putting 20g of the obtained solid landfill into 400mL of the acetic acid solution, oscillating for 18h at 25 ℃, filtering the supernatant, measuring the contents of Pb, Cr, Cu and As in the solid landfill by using an inductively coupled plasma emission spectrum, and calculating the fixed parts of the Pb, Cr, Cu and As to be 96.72%, 97.34%, 99.99% and 99.44% respectively. The results show that the fly ash from incineration of the household garbage and the high-concentration wastewater containing arsenic and heavy metal can be jointly stabilized.
It can be seen from the comparison between example 1 and example 2 that when 5000mg/L arsenic is added to the liquid to be treated, the immobilization rates of Pb, Cr and As in the solid landfill obtained are only reduced to a very small extent, indicating that the co-treatment of high-concentration arsenic does not have a significant effect on the original treatment and disposal of the fly ash from incineration of the municipal waste.
Example 3
The properties of the fly ash from incineration of household garbage were the same as in example 1.
The simulated arsenic-containing wastewater was the same as in example 2.
Adding fly ash into deionized water according to the ratio of 1kg to 20L2, oscillating at 25 deg.C and 150r/min for 24h, centrifuging to remove supernatant, placing the residue in an oven, and drying at 105 deg.C to constant weight to obtain enough water-washed pretreated fly ash.
Adding 100g of the washed and dried domestic garbage incineration fly ash into 100mL of simulated arsenic-containing wastewater, mixing, and stirring until solid and liquid are fully contacted;
then adding 100g of the household garbage incineration fly ash which is washed and dried, stirring until solid and liquid are fully contacted, and continuing stirring for 5 min;
standing for 24h, drying the obtained mixture at 65 ℃ to constant weight to obtain a solid landfill, and condensing and recovering liquid during drying;
preparing an acetic acid solution with the concentration of 0.1mol/L, putting 20g of the obtained solid landfill into 400mL of the acetic acid solution, oscillating for 18h at 25 ℃, filtering the supernatant, measuring the contents of Pb, Cr, Cu and As in the solid landfill by using an inductively coupled plasma emission spectrum, and calculating the fixed parts of the Pb, Cr, Cu and As to be 98.03%, 97.93%, 99.99% and 99.71% respectively. The result shows that the incineration fly ash of the household garbage and the high-concentration arsenic-containing wastewater can be jointly stable.
The comparison between the example 1 and the example 2 shows that the stability of Pb, Cr, Cu and As is improved to a certain extent after the water washing pretreatment.
Comparative example 1
The properties of the fly ash from incineration of household garbage were the same as in example 1.
The simulated arsenic-containing wastewater was the same as in example 2.
Firstly, 200g of domestic waste incineration fly ash is added into 100mL of simulated arsenic-containing wastewater at one time for mixing, the stirring is continued, the total stirring time is 5 times of that of the embodiment 2,
standing for 24h, and then drying the obtained mixture at 65 ℃ until the weight is constant to obtain a solid landfill;
preparing an acetic acid solution with the concentration of 0.1mol/L, putting 20g of the obtained solid landfill into 400mL of the acetic acid solution, oscillating for 18h at 25 ℃, filtering the supernatant, measuring the contents of Pb, Cr, Cu and As by using an inductively coupled plasma emission spectrum, and calculating the fixed parts of the Pb, Cr, Cu and As to be 87.09%, 79.47%, 82.53% and 89.91% respectively. The result shows that the fly ash and the arsenic-containing liquid are mixed for several times, which is a key factor for ensuring the stability of the finally obtained landfill and ensuring that the heavy metal is not easy to dissolve.
Comparative example 2
The properties of the fly ash from incineration of household garbage were the same as in example 1.
The simulated arsenic-containing wastewater was essentially the same as example 2, except for having a different pH, which in this comparative example was 10.
The rest is the same as example 2.
Filtering the supernatant, measuring the contents of Pb, Cr, Cu and As by inductively coupled plasma emission spectroscopy, and calculating the fixed parts of Pb, Cr, Cu and As to be 72.97%, 97.44%, 99.99% and 98.82% respectively. The result shows that on the basis of ensuring the properties of the fly ash, the solid-to-liquid ratio of the fly ash and the liquid to be treated and the mixing mode of the fly ash and the liquid to be treated, the initial pH of the liquid to be treated is another key factor for ensuring the stability of the finally obtained landfill and the difficulty in back dissolution of heavy metals.
Comparative example 3
The properties of the fly ash from incineration of household garbage were the same as in example 1.
The simulated arsenic-containing wastewater was essentially the same as example 2, except for having a different pH, which in this comparative example was 3.
The rest is the same as example 2.
Filtering the supernatant, measuring the contents of Pb, Cr, Cu and As by inductively coupled plasma emission spectrometry, and calculating the fixed parts of Pb, Cr, Cu and As to be respectively 92.12%, 90.34%, 92.29% and 93.67%. The result shows that on the basis of ensuring the properties of the fly ash, the solid-to-liquid ratio of the fly ash and the liquid to be treated and the mixing mode of the fly ash and the liquid to be treated, the initial pH of the liquid to be treated is another key factor for ensuring the stability of the finally obtained landfill and the difficulty in back dissolution of heavy metals.
Example 3
The properties of the fly ash from incineration of household garbage were the same as those of comparative example 1.
With Na 3 AsO 4 ·12H 2 O preparing the simulated arsenic-containing wastewater with the arsenic concentration of 2000mg/L, wherein the pH value is about 6 (the amplitude deviation is not more than 0.5).
Adding 90g of domestic waste incineration fly ash into 100mL of simulated arsenic-containing wastewater, mixing, and stirring until solid and liquid are fully contacted;
then adding 90g of domestic waste incineration fly ash, stirring for 10min until solid and liquid are fully contacted, and continuing stirring for 10 min;
standing for 18 h;
then drying the obtained mixture at 60 ℃ for 18h to constant weight to obtain a solid landfill, and condensing and recovering liquid during drying;
preparing an acetic acid solution with the concentration of 0.1mol/L, putting 20g of the obtained solid landfill into 400mL of the acetic acid solution, oscillating for 18h at 25 ℃, filtering the supernatant, measuring the contents of Pb, Cr, Cu and As in the solid landfill by using an inductively coupled plasma emission spectrum, and calculating the fixed parts of the Pb, Cr, Cu and As to be 97.72%, 98.44%, 99.23% and 99.11% respectively. The results show that the fly ash from incineration of the household garbage and the high-concentration wastewater containing arsenic and heavy metal can be jointly stabilized.
It can be seen from the comparison between example 1 and example 2 that the immobilization rates of Pb, Cr and As in the solid landfill obtained by adding 2000mg/L arsenic to the liquid to be treated are only reduced to a very small extent, indicating that the co-treatment of high-concentration arsenic does not have a significant effect on the original treatment and disposal of the fly ash from incineration of municipal waste.
Example 4
The properties of the fly ash from incineration of household garbage were the same as those of comparative example 1.
With Na 3 AsO 4 ·12H 2 O preparing simulated arsenic-containing wastewater with the arsenic concentration of 1000mg/L and the pH value of 8.
Firstly, adding 110g of domestic waste incineration fly ash into 100mL of simulated arsenic-containing wastewater, mixing, and stirring until solid and liquid are fully contacted;
then adding 110g of domestic waste incineration fly ash, stirring for 8min until solid and liquid are fully contacted, and continuing stirring for 8 min;
standing for 2 h;
then drying the obtained mixture at 70 ℃ for 24h to constant weight to obtain a solid landfill, and condensing and recovering liquid during drying;
preparing an acetic acid solution with the concentration of 0.1mol/L, putting 20g of the obtained solid landfill into 400mL of the acetic acid solution, oscillating for 18h at 25 ℃, filtering the supernatant, measuring the contents of Pb, Cr, Cu and As in the solid landfill by using an inductively coupled plasma emission spectrum, and calculating the fixed parts of the Pb, Cr, Cu and As to be 96.50%, 98.34%, 98.99% and 99.10% respectively. The results show that the fly ash from the incineration of the household garbage and the high-concentration wastewater containing arsenic and heavy metals can be jointly stabilized.
It can be seen from the comparison between example 1 and example 2 that the immobilization rates of Pb, Cr and As in the solid landfill obtained by adding 1000mg/L arsenic to the liquid to be treated are only reduced to a very small extent, indicating that the co-treatment of high-concentration arsenic does not have a significant effect on the original treatment and disposal of the fly ash from incineration of the municipal waste.
Claims (10)
1. A method for fixing arsenic in liquid by using fly ash to form safe landfill is characterized by comprising
1) Mixing fly ash with arsenic-containing liquid;
stirring; standing;
wherein,
adding the fly ash into the arsenic-containing liquid for N times, wherein N is more than or equal to 2;
the stirring time is 5-10 min;
the mixture obtained after the fly ash and the arsenic-containing liquid are mixed does not have fluidity in a standing state;
the standing time is 18-24 h;
2) separating to obtain solid landfill;
wherein, the separation treatment process is to separate the liquid part from the solid part in a gasification mode.
2. The method of utilizing fly ash to effect arsenic sequestration in liquids to form safe landfills according to claim 1,
2) wherein the separation process comprises
Heating at a certain temperature; or
Heating at a certain temperature, and condensing and recovering the evaporated liquid.
3. The method of utilizing fly ash to effect arsenic sequestration in liquids to form safe landfills according to claim 2,
2) and (3) keeping the heating state to constant weight at the heating temperature of 60-70 ℃, and finishing the treatment to obtain the solid landfill.
4. The method of utilizing fly ash to effect arsenic sequestration in liquids to form safe landfills according to claim 2,
in the step 1), fly ash and arsenic-containing liquid are mixed according to the solid-to-liquid ratio of 1.8-2.2 Kg: 1L;
in the step 1), the fly ash is added into the arsenic-containing liquid each time, and then the fly ash is stirred.
5. The method for fixation of arsenic in liquid to form safe landfill using fly ash as claimed in any one of claims 1 to 4,
the fly ash has a particle size of not more than 200 mu m, a bulk density of 0.5-1.0 g/cm, a water content of not more than 1.5%, and calcium hydroxide content of not less than 30 wt%.
6. The method of utilizing fly ash to effect arsenic sequestration in liquids to form safe landfills according to claim 5,
an arsenic-containing liquid, the liquid having an arsenic content of not more than 5000mg/L and having a pH of 5 to 8.
7. The method of utilizing fly ash to effect arsenic sequestration in liquids to form safe landfills according to claim 6,
the fly ash comprises metal elements and non-metal elements;
the metal elements comprise one or more of calcium, sodium, potassium, magnesium, zinc and aluminum;
the nonmetal elements comprise one or two of chlorine and silicon.
8. The method of utilizing fly ash to effect arsenic sequestration in liquids to form safe landfills according to claim 6,
the fly ash is a product after pretreatment, and the pretreatment process comprises the following steps:
mixing fly ash with deionized water; the solid-liquid ratio of the mixture is not higher than 1kg to 20L;
oscillating; the oscillation time is 18-24 h, and the frequency is 120-;
carrying out centrifugal separation;
drying; the drying temperature was 105. + -. 2 ℃.
9. The method of utilizing fly ash to effect arsenic sequestration in liquids to form safe landfills according to claim 6,
leaching the obtained solid landfill by using an acetic acid solution with the concentration of 0.1mol/L in a vibration treatment mode, and measuring the content of arsenic contained in the filtered supernatant by using an inductively coupled plasma emission spectrum;
the arsenic leaching of the resulting solid landfill was calculated to be less than 1%.
10. The method of utilizing fly ash to effect arsenic sequestration in liquids to form safe landfills according to claim 9,
the solid-liquid ratio of the acetic acid solution to the solid landfill is 1kg to 20L;
the room temperature of the leaching treatment is 25 +/-2 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648201A (en) * | 2009-05-13 | 2010-02-17 | 北京健坤伟华新能源科技有限公司 | Garbage burning flying dust treating system |
| CN101708499A (en) * | 2009-12-04 | 2010-05-19 | 同济大学 | Method for jointly stabilizing fly ash and arsenic-containing waste |
| CN102218428A (en) * | 2011-01-20 | 2011-10-19 | 杭州大地环保有限公司 | Treatment method of arsenic slag |
| US20130315804A1 (en) * | 2012-05-22 | 2013-11-28 | Fmc Wyoming Corporation | Fly Ash and Fly Ash Leachate Treatment |
| CN114210690A (en) * | 2021-12-17 | 2022-03-22 | 湖南军信环保股份有限公司 | Safe fly ash landfill method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648201A (en) * | 2009-05-13 | 2010-02-17 | 北京健坤伟华新能源科技有限公司 | Garbage burning flying dust treating system |
| CN101708499A (en) * | 2009-12-04 | 2010-05-19 | 同济大学 | Method for jointly stabilizing fly ash and arsenic-containing waste |
| CN102218428A (en) * | 2011-01-20 | 2011-10-19 | 杭州大地环保有限公司 | Treatment method of arsenic slag |
| US20130315804A1 (en) * | 2012-05-22 | 2013-11-28 | Fmc Wyoming Corporation | Fly Ash and Fly Ash Leachate Treatment |
| CN114210690A (en) * | 2021-12-17 | 2022-03-22 | 湖南军信环保股份有限公司 | Safe fly ash landfill method |
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