CN117123591B - Method for dry dechlorination of waste incineration fly ash and synchronous preparation of liquid chlorine and solidified soil - Google Patents
Method for dry dechlorination of waste incineration fly ash and synchronous preparation of liquid chlorine and solidified soil Download PDFInfo
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- 239000002689 soil Substances 0.000 title claims abstract description 111
- 239000010881 fly ash Substances 0.000 title claims abstract description 101
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004056 waste incineration Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000006298 dechlorination reaction Methods 0.000 title description 6
- 230000001360 synchronised effect Effects 0.000 title description 4
- 239000002910 solid waste Substances 0.000 claims abstract description 96
- 239000000463 material Substances 0.000 claims abstract description 75
- 239000010802 sludge Substances 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003546 flue gas Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 230000000382 dechlorinating effect Effects 0.000 claims abstract 2
- 239000007787 solid Substances 0.000 claims description 22
- 239000002893 slag Substances 0.000 claims description 11
- 239000003245 coal Substances 0.000 claims description 7
- 238000004043 dyeing Methods 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000003864 humus Substances 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 33
- 229910052801 chlorine Inorganic materials 0.000 abstract description 33
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 32
- 230000008569 process Effects 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000001784 detoxification Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 238000002386 leaching Methods 0.000 description 23
- 229910001385 heavy metal Inorganic materials 0.000 description 18
- 229910052742 iron Inorganic materials 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000010304 firing Methods 0.000 description 10
- 239000010813 municipal solid waste Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 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 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 229910000278 bentonite Inorganic materials 0.000 description 4
- 239000000440 bentonite Substances 0.000 description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000003841 chloride salts Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 239000010882 bottom ash Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
- 239000010806 kitchen waste Substances 0.000 description 1
- 238000012423 maintenance Methods 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
- 230000010355 oscillation Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/38—Stirring or kneading
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B2101/00—Type of solid waste
- B09B2101/30—Incineration ashes
Abstract
The invention discloses a method for dechlorinating waste incineration fly ash by a dry method and synchronously preparing liquid chlorine and solidified soil, which comprises the steps of mixing carbon-based solid waste, sludge solid waste and waste incineration fly ash, uniformly stirring, and grinding into powder to obtain a roasting fly ash primary material; mixing cohesive soil and a roasting fly ash primary material to obtain a cohesive roasting primary material; adding water into the mixture, uniformly stirring, granulating, and drying to obtain a roasting ball material; calcining the mixture, directly introducing flue gas generated by roasting into a cathode chamber of an electrolytic cell for electrolysis, condensing and liquefying gas recovered from an anode chamber to obtain liquid chlorine; meanwhile, cooling and grinding the ball material obtained after roasting into powder to obtain activated powder; adding water into the mixture, stirring the mixture uniformly, putting the mixture into solidified soil forming equipment to obtain a solidified soil green body, and naturally curing the solidified soil for 14 to 28 days to obtain solidified soil. The method has simple process, can realize the effective recycling of chlorine in the waste incineration fly ash by roasting and high-temperature electrolysis, and synchronously realize the detoxification of the waste incineration fly ash and the preparation of solidified soil.
Description
Technical Field
The invention belongs to the field of harmless disposal and resource utilization of dangerous wastes, and particularly relates to a method for dry dechlorination of waste incineration fly ash and synchronous preparation of liquid chlorine and solidified soil.
Background
With the improvement of the living standard of urban residents, the output of urban household garbage is obviously improved. Currently, the disposal of incineration of household waste is the most effective way to achieve reduction of waste. However, the household garbage incineration disposal can generate a certain amount of garbage incineration fly ash while realizing the reduction. The fly ash of the incineration of the household garbage is derived from the trapped matters of a flue gas purification system and the bottom ash settled at the bottom of a flue in the power generation process of the incineration of the household garbage, belongs to dangerous wastes which need important control in various countries, and is explicitly listed in the national dangerous waste directory (2021 edition) in China.
At present, the waste incineration fly ash is mainly treated by stabilizing landfill, which not only occupies a large amount of land resources, but also causes serious secondary environmental pollution. The content of chloride in the waste incineration fly ash is high, and the chlorine mainly comes from inorganic chloride in kitchen waste and organic chloride in the waste.
The existing electrolysis equipment in the chlor-alkali industry is not suitable for the enrichment and conversion of chlorine in fly ash slurry due to the limitation of the self structural characteristics and parameter setting, and cannot meet the high-efficiency treatment requirement of large amounts of chlorine-containing solid hazardous wastes. In particular, the current chlor-alkali industry electric equipment has very close distance between the cathode and the anode, a permeable membrane and a reverse osmosis membrane are fixedly arranged between the electrodes, the arrangement mode of a membrane assembly is complex, and the membrane assembly and the electrode assembly are required to be arranged in a laminated way. If the membrane module in the equipment is blocked, the membrane module cannot be easily detached, and in a serious case, the whole electric equipment is scrapped. At the same time, strict requirements are placed on the characteristics of the liquid being handled during operation of the electrically powered device.
Aiming at the urgent need of solving the problems in the industry, in order to realize the high-efficiency environmental safety of the fly ash disposal, and simultaneously realize the quality of the fly ash derivative product to meet the national standard, promote the fly ash disposal and the product popularization to be highly marketized, the technology of researching the dry dechlorination of the waste incineration fly ash, synchronously preparing liquid chlorine and realizing the recycling of the dechlorinated fly ash residue is urgent.
Disclosure of Invention
The invention aims to: the invention aims to provide a method for synchronously preparing liquid chlorine and solidified soil by dry dechlorination of waste incineration fly ash. The method has simple process, can realize the effective recycling of chlorine in the waste incineration fly ash by roasting and high-temperature electrolysis, and synchronously realize the detoxification of the waste incineration fly ash and the preparation of solidified soil.
The technical scheme is as follows: the aim of the invention is achieved by the following technical scheme:
the invention provides a method for dry dechlorination of waste incineration fly ash and synchronous preparation of liquid chlorine and solidified soil, which comprises the following steps:
(1) Mixing carbon-based solid waste, sludge solid waste and waste incineration fly ash, uniformly stirring, and grinding into powder to obtain a roasting fly ash primary material;
(2) Mixing cohesive soil with the roasting fly ash primary material obtained in the step (1) to obtain a cohesive roasting primary material;
(3) Adding water into the viscous roasting primary material obtained in the step (2), uniformly stirring, granulating, and drying to obtain a roasting ball material;
(4) Introducing the roasting ball material obtained in the step (3) into a roasting kiln for roasting, directly introducing flue gas generated by roasting into a cathode chamber of a high-temperature solid electrolytic cell for electrolysis after passing through a spiral separator, condensing and liquefying gas recovered from an anode chamber to obtain liquid chlorine;
(5) And naturally cooling the ball material obtained after roasting, and grinding the ball material into powder to obtain activated powder;
(6) Adding water into the activated powder obtained in the step (5), stirring uniformly, then adding into solidified soil forming equipment to obtain a solidified soil green body, and naturally curing for 14-28 days to obtain solidified soil.
The high temperature solid electrolytic cell (SOEC) used in the present invention is an electrolytic device having a solid electrolyte, which is efficient and can operate in a high temperature environment. The higher operating temperature makes the energy conversion efficiency of SOEC far superior to other electrolysis technologies. SOEC can directly utilize the heat of high-temperature flue gas and electrolyze gaseous substances to realize rapid electron migration, thereby promoting the efficient implementation of oxidation-reduction reaction.
Preferably, in the step (1), the mass ratio of the carbon-based solid waste to the sludge solid waste to the waste incineration fly ash is 15-45:20-40:100.
Further, in the step (1), the carbon-based solid waste is any one of printing and dyeing sludge, oil sludge and humus soil.
Further, in the step (1), the sludge solid waste is any one of fly ash, coal gangue, red mud, lithium slag or blast furnace slag.
Preferably, in the step (2), the mass ratio of the cohesive soil to the calcined fly ash primary material is 5-15:100.
Further, in the step (2), the cohesive soil is any one of clay, shale soil, bentonite or bentonite.
Preferably, in the step (3), the liquid-solid ratio of the water to the viscous roasting primary material is 25-45:100 mL/g.
Preferably, in the step (4), the calcination temperature is 550-1150 ℃, and the electrolysis voltage is 5-55 v.
Preferably, in the step (6), the liquid-solid ratio of the water to the activated powder is 20-40:100 mL/g.
Reaction mechanism:
in the roasting process, chloride in the household garbage incineration fly ash can permeate into the carbon-based solid waste and catalyze the decomposition of hydrocarbon in the carbon-based solid waste to generate hydrogen chloride and superheated water vapor, so that the carbonization of the carbon-based solid waste and the separation process of chlorine in the fly ash are accelerated. In a high-temperature environment, the newly generated carbon material can obviously reduce the activation energy of the reaction of hydrogen chloride and heavy metals, silicon, calcium, iron and the like in the fly ash, reduce the boiling point of generated chloride and increase the saturated vapor pressure of corresponding chlorinated products. Under the high-temperature roasting environment, the silicon-aluminum minerals in the sludge solid waste are easy to combine with calcium, iron, sodium and potassium in the fly ash to generate the cementing material with alkali excitation activity. Meanwhile, the combination process of the silicon-aluminum minerals in the sludge solid waste and the calcium, iron, sodium and potassium in the fly ash can promote the release of chlorine, and hydrogen chloride and hypochlorous acid are generated by combining water vapor. Hypochlorous acid and superheated steam can further react with silicon-aluminum base in the sludge solid waste under the carbothermal chlorination effect, so that the cementing material is activated and chloride is released again. The flue gas generated by roasting is directly led into a cathode chamber of a high-temperature solid electrolytic cell for electrolysis after passing through a spiral separator, chloride releases chloride ions on the surface of a cathode electrode of the cathode chamber, and the chloride ions pass through a solid electrolyte to reach the surface of an anode chamber under the action of potential difference to lose electrons so as to generate chlorine. The activated powder obtained after roasting can be subjected to hydration reaction and geopolymerization reaction with water, and solidified soil with certain strength is formed under the conditions of compaction and maintenance.
Advantageous effects
The method has simple process, can realize the effective recycling of chlorine in the waste incineration fly ash by roasting and high-temperature electrolysis, and synchronously realize the detoxification of the waste incineration fly ash and the preparation of solidified soil, wherein the purity (volume fraction of chlorine) of the prepared liquid chlorine is higher than 98%, the chlorine content of the prepared solidified soil is lower than 1.3%, the leaching concentration of heavy metal in the prepared solidified soil is lower than 0.01mg/L, and the strength of the solidified soil can reach 8.9MPa.
Drawings
FIG. 1 is a flow chart of the method of the present invention.
Detailed Description
The technical scheme of the present invention is described in detail below through specific examples, but the scope of the present invention is not limited to the examples.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase through regular channels, with no manufacturer noted.
The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials used in the examples described below, unless otherwise specified, are all commercially available products.
The flow chart of the method of the invention is shown in fig. 1, and the technical scheme of the invention is further described with reference to fig. 1.
Waste incineration fly ash: is provided by Jiangsu ordinary second household garbage incineration power plant company and mainly comprises 36.2 percent of CaO, 23.9 percent of Cl and 11.0 percent of SO 3 、11.6%Na 2 O、6.33%K 2 O、4.38%SiO 2 、1.40%Fe 2 O 3 、1.25%Al 2 O 3 And other components (loss on ignition and other unavoidable impurities).
Example 1 influence of carbon-based solid waste, sludge solid waste, waste incineration fly ash Mass ratio on the Property of the prepared solidified soil and liquid chlorine
The method comprises the steps of weighing carbon-based solid waste, sludge solid waste and waste incineration, mixing, uniformly stirring and grinding fly ash into powder according to mass ratios of 7.5:20:100, 10:20:100, 12.5:20:100, 15:12.5:100, 15:15:100, 15:17.5:100, 15:20:100, 30:20:100, 45:20:100, 15:30:100, 30:40:100, 45:40:100, 45:42.5:100, 45:45:100, 45:47.5:100, 47.5:40:100, 50:40:100 and 52.5:40:100 respectively, and obtaining a baked fly ash primary material, wherein the carbon-based solid waste is printing and dyeing sludge solid waste, and the sludge solid waste is fly ash.
Carbon-based solid waste: the dyeing sludge is provided by Shaoxing Ke Qiaomou dyeing enterprises, and the chemical components of the dyeing sludge mainly comprise 45.87% SO 3 、39.25%Fe 2 O 3 、6.72%SiO 2 、5.04%Al 2 O 3 1.47% CaO and other components (loss on ignition and other unavoidable impurities);
solid waste of sludge: fly ash from Taiku power plant of International electric Co Ltd, mainly comprising 43.21% SiO 2 、27.08%Al 2 O 3 、15.62%Fe 2 O 3 、6.58%CaO、3.42%TiO 2 、1.43%SO 3 、1.04%K 2 O、0.63% Na 2 O and other components (unavoidable impurities and loss on ignition);
mixing cohesive soil and the calcined fly ash primary material according to a mass ratio of 5:100, and mixing to obtain the cohesive calcined primary material, wherein the cohesive soil is clay. Adding water into the viscous roasting primary material according to the liquid-solid ratio of 25:100mL/g, uniformly stirring, granulating, and drying to obtain the roasting ball material. The roasting ball material is led into a roasting kiln for roasting, flue gas generated by roasting is directly led into a cathode chamber of a high-temperature solid electrolytic cell (Shanghai preamble experimental equipment, model: SHQY GW-01) for electrolysis, and gas recovered from an anode chamber is condensed and liquefied to obtain liquid chlorine, wherein the roasting temperature is 550 ℃, and the electrolysis voltage is 5V; and naturally cooling the ball material obtained after roasting, and grinding the ball material into powder to obtain the activated powder. Adding water into the activated powder according to the liquid-solid ratio of 20:100mL/g, stirring uniformly, then adding into solidified soil forming equipment to obtain a solidified soil green body, and naturally curing for 14 days to obtain solidified soil.
Compressive strength test: the compressive strength test of the cured soil prepared by the invention is carried out according to the standard of concrete solid bricks (GB/T21144-2007).
Preparing leaching liquid: the leaching solution for preparing the solidified soil is prepared according to the horizontal oscillation method of solid waste leaching toxicity leaching method (HJ 557-2010).
And (3) measuring the concentration of heavy metal ions in the solidified soil leaching solution:
the concentration of lead pollutant in the leaching solution is measured according to the specification of inductively coupled plasma emission spectrometry (HJ 776-2015) for measuring 32 elements in water quality.
The total chromium in the solidified soil leaching solution is measured according to the specification of flame atomic absorption spectrophotometry for measuring water quality chromium (HJ 757-2015).
Determination of liquid chlorine purity: the purity of the liquid chlorine (volume fraction of chlorine) was measured according to Industrial liquid chlorine (GB/T5138-2021).
Determination of chlorine content: the chlorine content in the solidified soil was measured according to the "sand for building" (GB/T14684-2011). The results are shown in Table 1.
TABLE 1 influence of mass ratio of carbon-based solid wastes, sludge solid wastes, and waste incineration fly ash on the properties of the prepared solidified soil and liquid chlorine
As can be seen from table 1, when the mass ratio of the carbon-based solid waste, the sludge solid waste, and the waste incineration fly ash is less than 15:20:100 (as in table 1, the mass ratio of the carbon-based solid waste, the sludge solid waste, and the waste incineration fly ash is 12.5:20:100, 10:20:100, 7.5:20:100, 15:17.5:100, 15:15:100, 15:12.5:100, and the lower ratio not listed in table 1), the addition amounts of the carbon-based solid waste and the sludge solid waste are small, the material reaction is unbalanced, the leaching concentration of heavy metal and the chlorine content of the prepared solidified soil are significantly increased as the mass ratio of the carbon-based solid waste, the sludge solid waste, and the waste incineration fly ash is reduced, and the uniaxial compression strength and the liquid chlorine purity of the prepared solidified soil are significantly reduced as the mass ratio of the carbon-based solid waste, the sludge solid waste, and the waste incineration fly ash is reduced. When the mass ratio of the carbon-based solid waste, the sludge solid waste and the waste incineration fly ash is 15-45:20-40:100 (as in table 1, the mass ratio of the carbon-based solid waste, the sludge solid waste and the waste incineration fly ash is 15:20:100, 30:20:100, 45:20:100, 15:30:100, 30:30:100, 45:30:100, 15:40:100, 30:40:100 and 45:40:100), chloride salts in the household garbage incineration fly ash can permeate into the carbon-based solid waste and catalyze the decomposition of hydrocarbons in the carbon-based solid waste to generate hydrogen chloride and superheated water gas in the roasting process, so that the carbonization of the carbon-based solid waste and the separation of chlorine in the fly ash are accelerated. In a high-temperature environment, the newly generated carbon material can obviously reduce the activation energy of the reaction of hydrogen chloride and heavy metals, silicon, calcium, iron and the like in the fly ash, reduce the boiling point of generated chloride and increase the saturated vapor pressure of corresponding chlorinated products. Under the high-temperature roasting environment, the silicon-aluminum minerals in the sludge solid waste are easy to combine with calcium, iron, sodium and potassium in the fly ash to generate the cementing material with alkali excitation activity. Meanwhile, the combination process of the silicon-aluminum minerals in the sludge solid waste and the calcium, iron, sodium and potassium in the fly ash can promote the release of chlorine, and hydrogen chloride and hypochlorous acid are generated by combining water vapor. Hypochlorous acid and superheated steam can further react with silicon-aluminum base in the sludge solid waste under the carbothermal chlorination effect, so that the cementing material is activated and chloride is released again. Finally, the chlorine content of the prepared solidified soil is lower than 1.3%, the leaching concentration of heavy metals is lower than 0.01mg/L, the strength of the solidified soil is higher than 5.4MPa, and the purity of liquid chlorine is higher than 98.4%. When the mass ratio of carbon-based solid waste, sludge solid waste, and waste incineration fly ash is greater than 45:40:100 (as in table 1, the mass ratio of carbon-based solid waste, sludge solid waste, and waste incineration fly ash is 45:42.5:100, 45:45:100, 45:47.5:100, 47.5:40:100, 50:40:100, and 52.5:40:100, and higher ratios not listed in table 1), the carbon-based solid waste and sludge solid waste are added in excess, the material reaction is unbalanced, resulting in a significant increase in both the heavy metal leaching concentration and chlorine content of the prepared solidified soil as the mass ratio of carbon-based solid waste, sludge solid waste, and waste incineration fly ash is further increased, and the single-axis compressive strength and liquid chlorine purity of the prepared solidified soil are both significantly reduced as the mass ratio of carbon-based solid waste, sludge solid waste, and waste incineration fly ash is further increased.
Therefore, in general, when the mass ratio of the carbon-based solid waste to the sludge solid waste to the waste incineration fly ash is 15-45:20-40:100, the method is most beneficial to improving the performance of the prepared solidified soil and liquid chlorine.
EXAMPLE 2 influence of the mass ratio of the cohesive soil to the calcined fly ash on the Properties of the prepared solidified soil and liquid chlorine
And respectively weighing carbon-based solid waste, sludge solid waste and waste incineration fly ash according to a mass ratio of 45:40:100, mixing, uniformly stirring, and grinding into powder to obtain a roasting fly ash primary material, wherein the carbon-based solid waste is oil sludge, and the sludge solid waste is coal gangue.
Carbon-based solid waste: the sludge was obtained from a petroleum refinery of Shaanxi and contains 34.51% extract oil, 21.73% heavy oil, 27.44% slag and 16.32% water.
Solid waste of sludge: coal gangue: from Shanxi mountain coal electric Co., ltd, mainly comprising 46.87% SiO 2 、33.51%Al 2 O 3 、12.04%Fe 2 O 3 、2.72%CaO、2.36K 2 O、1.37%TiO 2 And other components (unavoidable impurities and loss on ignition).
Mixing cohesive soil and a roasted fly ash primary material according to the mass ratio of 2.5:100, 3:100, 4:100, 5:100, 10:100, 15:100, 17:100, 19:100 and 20:100, and mixing to obtain the cohesive roasting primary material, wherein the cohesive soil is shale soil. Adding water into the viscous roasting primary material according to the liquid-solid ratio of 35:100mL/g, uniformly stirring, granulating, and drying to obtain the roasting ball material. The roasting ball material is led into a roasting kiln for roasting, the flue gas generated by roasting is directly led into a cathode chamber of a high-temperature solid electrolytic cell for electrolysis after passing through a spiral separator, and the gas recovered from an anode chamber is condensed and liquefied to obtain liquid chlorine, wherein the roasting temperature is 850 ℃, and the electrolysis voltage is 30V; and naturally cooling the ball material obtained after roasting, and grinding the ball material into powder to obtain the activated powder. Adding water into the activated powder according to the liquid-solid ratio of 30:100mL/g, stirring uniformly, then adding into solidified soil forming equipment to obtain a solidified soil green body, and naturally curing for 21 days to obtain solidified soil.
The compressive strength test, the preparation of the leaching solution, the measurement of the concentration of heavy metal ions in the solidified soil leaching solution, the measurement of the purity of liquid chlorine and the measurement of the chlorine content are all the same as in example 1, and the results of this example are shown in table 2.
TABLE 2 influence of the mass ratio of cohesive soil to calcined fly ash on the Properties of the prepared solidified soil and liquid chlorine
As can be seen from table 2, when the mass ratio of the cohesive soil to the calcined fly ash is less than 5:100 (as in table 2, the mass ratio of the cohesive soil to the calcined fly ash is 4:100, 3:100, 2.5:100, and the lower ratio not listed in table 2), the addition amount of the cohesive soil is small, the material reaction is unbalanced, so that the leaching concentration and chlorine content of the prepared solidified soil heavy metal are both significantly increased along with the decrease of the mass ratio of the cohesive soil to the calcined fly ash, and the uniaxial compressive strength and the liquid chlorine purity of the prepared solidified soil are both significantly decreased along with the decrease of the mass ratio of the cohesive soil to the calcined fly ash. When the mass ratio of the cohesive soil to the baked fly ash is 5-15:100 (as shown in table 2, when the mass ratio of the cohesive soil to the baked fly ash is 5:100, 10:100 and 15:100), in the baking process, chloride salt in the household garbage incineration fly ash can permeate into carbon-based solid waste and catalyze the decomposition of hydrocarbon in the carbon-based solid waste to generate hydrogen chloride and superheated water vapor, so that carbonization of the carbon-based solid waste and separation of chlorine in the fly ash are accelerated. In a high-temperature environment, the newly generated carbon material can obviously reduce the activation energy of the reaction of hydrogen chloride and heavy metals, silicon, calcium, iron and the like in the fly ash, reduce the boiling point of generated chloride and increase the saturated vapor pressure of corresponding chlorinated products. Under the high-temperature roasting environment, the silicon-aluminum minerals in the sludge solid waste are easy to combine with calcium, iron, sodium and potassium in the fly ash to generate the cementing material with alkali excitation activity. Meanwhile, the combination process of the silicon-aluminum minerals in the sludge solid waste and the calcium, iron, sodium and potassium in the fly ash can promote the release of chlorine, and hydrogen chloride and hypochlorous acid are generated by combining water vapor. Hypochlorous acid and superheated steam can further react with silicon-aluminum base in the sludge solid waste under the carbothermal chlorination effect, so that the cementing material is activated and chloride is released again. Finally, the chlorine content of the prepared solidified soil is lower than 0.7%, and the leaching concentration of heavy metals is lower than 5.2 multiplied by 10 -3 The strength of the solidified soil is higher than 7.2MPa, and the purity of the liquid chlorine is higher than 99.5 percent. When cohesive soil andwhen the mass ratio of the calcined fly ash primary material is greater than 15:100 (as in table 2, when the mass ratio of the cohesive soil to the calcined fly ash primary material is 17:100, 19:100, 20:100, and higher ratios not listed in table 2), the cohesive soil is excessively added, the material reaction is unbalanced, so that the heavy metal leaching concentration and the chlorine content of the prepared solidified soil are obviously increased along with the further increase of the mass ratio of the cohesive soil to the calcined fly ash primary material, and the uniaxial compressive strength and the liquid chlorine purity of the prepared solidified soil are obviously reduced along with the further increase of the mass ratio of the cohesive soil to the calcined fly ash primary material.
Therefore, in general, when the mass ratio of the cohesive soil to the calcined fly ash is 5-15:100, the prepared solidified soil and liquid chlorine performance can be improved most favorably.
EXAMPLE 3 Effect of calcination temperature on the Properties of the prepared solidified soil and liquid chlorine
And respectively weighing carbon-based solid waste, sludge solid waste and waste incineration fly ash according to a mass ratio of 45:40:100, mixing, uniformly stirring, and grinding into powder to obtain a roasting fly ash primary material, wherein the carbon-based solid waste is humus soil, and the sludge solid waste is red mud.
Carbon-based solid waste: humus soil is from Sichuan Kaires Hua Feng biotechnology Co., ltd, brand Kaires Hua Feng, 15L general humus soil;
solid waste of sludge: the red mud is from Shandong certain alumina Co Ltd and mainly comprises 23.94% of Al 2 O 3 、21.65%Fe 2 O 3 、16.74%SiO 2 、14.13%CaO、6.24% Na 2 O、5.28%TiO 2 And other components (unavoidable impurities and loss on ignition).
Mixing cohesive soil and the calcined fly ash primary material according to the mass ratio of 15:100, and obtaining the cohesive calcined primary material, wherein the cohesive soil is bentonite. Adding water into the viscous roasting primary material according to the liquid-solid ratio of 45:100mL/g, uniformly stirring, granulating, and drying to obtain the roasting ball material. The roasting ball material is led into a roasting kiln for roasting, flue gas generated by roasting is directly led into a cathode chamber of a high-temperature solid electrolytic cell for electrolysis after passing through a spiral separator, and gas recovered from an anode chamber is condensed and liquefied to obtain liquid chlorine, wherein the roasting temperature is 475 ℃, 500 ℃, 525 ℃, 550 ℃, 850 ℃, 1150 ℃, 1175 ℃, 1200 ℃, 1250 ℃ and the electrolysis voltage is 55V; and naturally cooling the ball material obtained after roasting, and grinding the ball material into powder to obtain the activated powder. Adding water into the activated powder according to the liquid-solid ratio of 40:100mL/g, stirring uniformly, then adding into solidified soil forming equipment to obtain a solidified soil green body, and naturally curing for 28 days to obtain solidified soil.
The compressive strength test, the preparation of the leaching solution, the measurement of the concentration of heavy metal ions in the solidified soil leaching solution, the measurement of the purity of liquid chlorine and the measurement of the chlorine content are all the same as in example 1, and the results of this example are shown in Table 3.
TABLE 3 influence of calcination temperature on the properties of the prepared solidified soil and liquid chlorine
As can be seen from table 3, when the firing temperature is less than 550 ℃ (as in table 3, the firing temperature is 525 ℃, 500 ℃, 475 ℃ and lower values not listed in table 3), the firing temperature is lower, the material reaction is unbalanced, resulting in that the heavy metal leaching concentration and chlorine content of the prepared solidified soil are both significantly increased with the decrease of the firing temperature, and the uniaxial compressive strength and liquid chlorine purity of the prepared solidified soil are both significantly decreased with the decrease of the firing temperature. When the roasting temperature is 550-1150 ℃ (as in table 3, the roasting temperature is 550 ℃, 850 ℃ and 1150 ℃), during the roasting process, chloride salt in the household garbage incineration fly ash can permeate into the carbon-based solid waste and catalyze the decomposition of hydrocarbon in the carbon-based solid waste to generate hydrogen chloride and superheated water vapor, so that the carbonization of the carbon-based solid waste and the separation of chlorine in the fly ash are accelerated. In a high-temperature environment, the newly generated carbon material can obviously reduce the activation energy of the reaction of hydrogen chloride and heavy metals, silicon, calcium, iron and the like in the fly ash, reduce the boiling point of generated chloride and increase the saturated vapor pressure of corresponding chlorinated products. Under the high-temperature roasting environment, the silicon-aluminum minerals in the sludge solid waste are easy to combine with calcium, iron, sodium and potassium in the fly ash to generate the cementing material with alkali excitation activity. Meanwhile, the combination process of the silicon-aluminum minerals in the sludge solid waste and the calcium, iron, sodium and potassium in the fly ash can promote the release of chlorine, and hydrogen chloride and hypochlorous acid are generated by combining water vapor. At the position ofUnder the action of carbothermal chlorination, hypochlorous acid and superheated water gas can further react with silicon-aluminum base in the sludge solid waste, so that the cementing material is activated and chloride is released again. Finally, the chlorine content of the prepared solidified soil is lower than 0.5%, and the leaching concentration of heavy metals is lower than 9.2 multiplied by 10 -4 The strength of the solidified soil is higher than 8.1MPa, and the purity of the liquid chlorine is higher than 99.6 percent. When the firing temperature is greater than 1150 ℃ (as in table 3, the firing temperature 1175 ℃, 1200 ℃, 1250 ℃, and higher values not listed in table 3), the firing temperature is too high, the material reaction is unbalanced, resulting in a significant increase in both heavy metal leaching concentration and chlorine content of the produced solidified soil with further increase in the firing temperature, and a significant decrease in both uniaxial compressive strength and liquid chlorine purity of the produced solidified soil with further increase in the firing temperature.
Therefore, in general, when the roasting temperature is 550-1150 ℃, the method is most beneficial to improving the performance of the prepared solidified soil and liquid chlorine.
Example 4 effect of sludge solid waste type on the Properties of the solidified soil and liquid chlorine prepared
And respectively weighing carbon-based solid waste, sludge solid waste and waste incineration fly ash according to a mass ratio of 45:100, mixing, uniformly stirring and grinding into powder to obtain a roasting fly ash primary material, wherein the carbon-based solid waste is printing and dyeing sludge, and the sludge solid waste is any one of fly ash, coal gangue, red mud, lithium slag and blast furnace slag.
Solid waste of sludge: the lithium slag comes from a new energy industry base of Yichun lithium battery, mainly comprising: 57.94% SiO 2 、24.57%Al 2 O 3 、6.15%CaO、7.24%SO 3 、0.45%K 2 O、0.62%Na 2 O、0.21%MgO、1.23%Fe 2 O 3 And other components (unavoidable impurities and loss on ignition);
blast furnace slag is from Longteng Steel Co., ltd, and mainly comprises 42.21% CaO, 37.52% SiO 2 、10.05%Al 2 O 3 、4.62%MgO、2.39%TiO 2 、2.45%SO 3 And other components (unavoidable impurities and loss on ignition).
Mixing cohesive soil and the calcined fly ash primary material according to the mass ratio of 15:100, and mixing to obtain the cohesive calcined primary material, wherein the cohesive soil is bentonite. Adding water into the viscous roasting primary material according to the liquid-solid ratio of 45:100mL/g, uniformly stirring, granulating, and drying to obtain the roasting ball material. The roasting ball material is led into a roasting kiln for roasting, the flue gas generated by roasting is directly led into a cathode chamber of a high-temperature solid electrolytic cell for electrolysis after passing through a spiral separator, and the gas recovered from an anode chamber is condensed and liquefied to obtain liquid chlorine, wherein the roasting temperature is 1150 ℃, and the electrolysis voltage is 55V; and naturally cooling the ball material obtained after roasting, and grinding the ball material into powder to obtain the activated powder. Adding water into the activated powder according to the liquid-solid ratio of 40:100mL/g, stirring uniformly, then adding into solidified soil forming equipment to obtain a solidified soil green body, and naturally curing for 28 days to obtain solidified soil.
The compressive strength test, the preparation of the leaching solution, the measurement of the concentration of heavy metal ions in the solidified soil leaching solution, the measurement of the purity of liquid chlorine and the measurement of the chlorine content are all the same as in example 1, and the results of this example are shown in Table 4.
TABLE 4 influence of sludge solid waste type on the properties of the prepared solidified soil and liquid chlorine
As can be seen from Table 4, when the solid waste of the sludge is any one of fly ash, coal gangue, red mud, lithium slag and blast furnace slag, the prepared solidified soil has close performance to liquid chlorine.
As described above, although the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limiting the invention itself. Various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The method for dechlorinating the waste incineration fly ash by a dry method and synchronously preparing liquid chlorine and solidified soil is characterized by comprising the following steps of:
(1) Mixing carbon-based solid waste, sludge solid waste and waste incineration fly ash, uniformly stirring, and grinding into powder to obtain a roasting fly ash primary material;
(2) Mixing cohesive soil with the roasting fly ash primary material obtained in the step (1) to obtain a cohesive roasting primary material;
(3) Adding water into the viscous roasting primary material obtained in the step (2), uniformly stirring, granulating, and drying to obtain a roasting ball material;
(4) Introducing the roasting ball material obtained in the step (3) into a roasting kiln for roasting, directly introducing flue gas generated by roasting into a cathode chamber of a high-temperature solid electrolytic cell for electrolysis after passing through a spiral separator, condensing and liquefying gas recovered from an anode chamber, and obtaining liquid chlorine;
(5) And naturally cooling the ball material after calcination, and grinding the ball material into powder to obtain activated powder;
(6) Adding water into the activated powder obtained in the step (5), uniformly stirring, then, adding into solidified soil forming equipment to obtain a solidified soil green body, and naturally curing for 14-28 days to obtain solidified soil;
in the step (1), the mass ratio of the carbon-based solid waste to the sludge solid waste to the waste incineration fly ash is 15-45:20-40:100;
in the step (1), the carbon-based solid waste is any one of printing and dyeing sludge, oil sludge or humus soil;
in the step (1), the sludge solid waste is any one of fly ash, coal gangue, red mud, lithium slag or blast furnace slag;
in the step (2), the mass ratio of the cohesive soil to the calcined fly ash primary material is 5-15:100.
2. The method of claim 1, wherein in step (2), the cohesive soil is any one of clay or shale.
3. The method of claim 1, wherein in the step (3), the liquid-solid ratio of the water to the viscous baking raw material is 25-45:100 ml/g.
4. The method according to claim 1, wherein in the step (4), the calcination temperature is 550-1150 ℃ and the electrolysis voltage is 5-55 v.
5. The method of claim 1, wherein in step (6), the liquid-to-solid ratio of water to activated powder is 20-40:100 ml/g.
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