CN117066256B - Harmless resource utilization method for waste incineration fly ash - Google Patents
Harmless resource utilization method for waste incineration fly ash Download PDFInfo
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- CN117066256B CN117066256B CN202311310477.5A CN202311310477A CN117066256B CN 117066256 B CN117066256 B CN 117066256B CN 202311310477 A CN202311310477 A CN 202311310477A CN 117066256 B CN117066256 B CN 117066256B
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- 239000010881 fly ash Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000004056 waste incineration Methods 0.000 title claims abstract description 33
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 54
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- 238000005554 pickling Methods 0.000 claims description 43
- 229920002125 Sokalan® Polymers 0.000 claims description 38
- 239000004584 polyacrylic acid Substances 0.000 claims description 38
- 238000004064 recycling Methods 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 229920000881 Modified starch Polymers 0.000 claims description 24
- 235000019426 modified starch Nutrition 0.000 claims description 24
- 239000002738 chelating agent Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- 229920002472 Starch Polymers 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 235000019698 starch Nutrition 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000008107 starch Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 11
- 239000007790 solid phase Substances 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 8
- FIQBJLHOPOSODG-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]benzoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=CC=C1C(O)=O FIQBJLHOPOSODG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- -1 3-propenylrhodanine Chemical compound 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000010882 bottom ash Substances 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 4
- 239000002920 hazardous waste Substances 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000001784 detoxification Methods 0.000 abstract 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 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 150000002500 ions Chemical class 0.000 description 24
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 23
- 230000000694 effects Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000010813 municipal solid waste Substances 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 239000003607 modifier Substances 0.000 description 8
- 238000007605 air drying Methods 0.000 description 6
- 229910001422 barium ion Inorganic materials 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- BYZDRRAHLZZRGC-UHFFFAOYSA-N ethyl 2-(2-methylprop-2-enoylperoxycarbonyl)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OOC(=O)C(C)=C BYZDRRAHLZZRGC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000185 dioxinlike effect Effects 0.000 description 2
- 150000002013 dioxins Chemical class 0.000 description 2
- 239000010791 domestic waste Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/30—Incineration ashes
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a harmless resource utilization method of waste incineration fly ash, and relates to the field of waste treatment. The hazardous waste of the waste incineration fly ash is treated by the method, dioxin is removed from the treated fly ash through medium-temperature pyrolysis, and heavy metal is removed through acid washing, so that complete detoxification is realized, the hazardous waste property of the fly ash can be removed through toxicity authentication, and the fly ash and bottom ash enter a building material utilization system together.
Description
Technical Field
The invention belongs to the technical field of garbage disposal, and particularly relates to a harmless recycling method of garbage incineration fly ash.
Background
At present, china follows the basic principles of innocuous treatment, reduction and recycling of municipal solid waste, the waste incineration technology is an effective method for treating the municipal solid waste, and generally, the waste incineration technology can reduce the volume of the treated domestic waste by 90% and the weight of the treated domestic waste by more than 80%, and can utilize combustible substances and biomass resources in the waste to generate heat energy and electric energy. Refuse incineration will play an increasingly important role in the aspect of refuse disposal in China. The most main problem of the waste incineration is that secondary pollution is possibly caused, and the waste incineration fly ash is a main carrier for secondary pollution, wherein high-concentration heavy metals, dioxin and other toxic and harmful substances are enriched.
Fly ash is a powder material with lighter volume weight and fine particle size, which is collected at a flue gas pipeline, a flue gas purification device, a separator device, a dust remover device and the like in the garbage incineration process. The fly ash contains organic pollutants such as benzopyrene, benzanthracene, dioxin and the like and heavy metals such as Cr, cd, hg, pb, cu, ni and the like.
At present, the widely accepted mode for recycling the fly ash is to wash the fly ash and then enter a cement burning kiln for cooperative treatment. And little research and application is done on the in situ disposal of fly ash. In view of uneven distribution of cement kilns in China, the situation that the cement kilns cannot be washed in various places is likely to be faced. It is therefore necessary to seek a method route for the in situ disposal of fly ash within a waste incineration plant.
Disclosure of Invention
The invention aims to provide a harmless recycling method of waste incineration fly ash, which has good removal effect on dioxin and heavy metal ions and realizes recycling of the fly ash.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a harmless resource utilization method of waste incineration fly ash comprises the following steps:
step one, pyrolyzing fly ash at low temperature;
step two, pickling is carried out by using pickling solution;
step three, solid-liquid separation;
step four, recycling the solid phase;
and fifthly, adding sodium sulfate into the liquid phase, separating solid from liquid, recycling 85-95% of acid liquor, removing heavy metals from the residual acid liquor through the heavy metal chelating agent, and discharging the residual acid liquor out of the system.
The method can lead the pollutant fly ash generated by the garbage incineration to be recycled; provides a disposal path with feasible technology and better cost for fly ash reclamation; the fly ash is treated in situ, so that the cost in the process of conveying the fly ash is reduced, and the risks of dust emission and the like in the process of transporting the fly ash can be effectively prevented; the fly ash is completely detoxified by removing heavy metals and dioxin, so that the fly ash is free from dangerous waste property; in addition, the recycled acid liquor greatly solves the problem of acid washing cost.
Specifically, the harmless and recycling method for the waste incineration fly ash comprises the following steps:
step one, introducing fly ash into a hearth in a nitrogen atmosphere, keeping the temperature at 400-500 ℃, detoxication is carried out on the fly ash, and the detoxified gas returns to the incineration hearth;
step two, pickling the waste incineration fly ash by using pickling solution; fully mixing and stirring to dissolve heavy metals in the fly ash into acid liquor, and dissolving calcium at the same time;
step three, solid-liquid separation is carried out;
step four, after naturally air-drying the solid phase after solid-liquid separation, adding the solid phase into bottom ash after garbage incineration, and carrying out recycling and building material utilization;
adding sodium sulfate into the liquid phase after solid-liquid separation, performing solid-liquid separation again, and drying and crushing the solid phase to obtain a pin; 85-95% of the liquid phase is returned to the pickling solution, and the residual liquid phase is filtered and discharged out of the system after heavy metals are removed by the heavy metal chelating agent.
According to one embodiment of the invention, the pH of the pickling solution is < 2.64.
According to one embodiment of the present invention, the pickling solution contains hydrochloric acid.
According to one specific embodiment of the invention, the mass-to-volume ratio of the fly ash to the pickling solution is as follows: 1g, 1.4-2mL.
According to one embodiment of the invention, the pickling time is 10-20min.
According to one specific embodiment of the invention, the mass ratio of the fly ash to the sodium sulfate is as follows: 1:0.25-0.4.
According to one embodiment of the present invention, the heavy metal chelating agent comprises a starch derivative.
According to one specific embodiment of the invention, the treatment time of the heavy metal chelating agent is 30-80min, and the dosage of the heavy metal chelating agent is 0.5-1.5g/L.
The invention also discloses a preparation method of the starch derivative, which comprises the following steps: the starch derivative is prepared by grafting reaction of phthalic acid mono-2- (methacryloyloxy) ethyl ester and starch.
The invention provides a preparation method of a starch derivative, which adopts phthalic acid mono-2- (methacryloyloxy) ethyl ester as a modifier to graft and modify starch, and the prepared starch derivative is used as a heavy metal chelating agent and has good effect of removing heavy metal ions.
Specifically, the preparation method of the starch derivative comprises the following steps:
adding starch into deionized water, adding an emulsifying agent, stirring and mixing uniformly, adding mono-2- (methacryloyloxy) ethyl phthalate and potassium persulfate, reacting at 55-70 ℃ for 40-70min, demulsifying with ethanol, drying, and extracting with acetone to obtain starch derivative.
According to one embodiment of the invention, the mass-to-volume ratio of the starch to the deionized water is as follows: 1g, 25-35mL. According to one embodiment of the invention, the mass ratio of the starch to the emulsifier is as follows: 1:0.03-0.08.
According to one embodiment of the invention, the mass ratio of the starch to the mono-2- (methacryloyloxy) ethyl phthalate is: 1:3.5-5.
According to one embodiment of the present invention, the concentration of the potassium persulfate in the reaction solution is 5.5 to 7mmol/L.
According to one embodiment of the invention, the emulsifier is an OP-10 emulsifier.
The invention also discloses the application of the starch derivative prepared by the preparation method in harmless recycling of the waste incineration fly ash.
The invention also discloses the application of the starch derivative prepared by the preparation method in heavy metal ion removal.
In order to further promote harmless recycling of the waste incineration fly ash, the invention also adds polyacrylic acid derivatives into the pickling solution.
According to one specific embodiment of the invention, in the pickling solution, the mass ratio of the polyacrylic acid derivative to the hydrochloric acid is as follows: 1:1.5-2.
The invention also discloses a preparation method of the polyacrylic acid derivative, which comprises the following steps: the polyacrylic acid derivative is prepared by adopting 3-propenylrhodanine to carry out grafting reaction with acrylic acid.
The invention provides a preparation method of a polyacrylic acid derivative, which uses 3-propenolignan as a modifier, wherein the prepared polyacrylic acid derivative is used in pickling solution, and the obtained pickling solution has good eluting effect on heavy metal ions and dioxin in fly ash.
Specifically, the preparation method of the polyacrylic acid derivative comprises the following steps: adding acrylic acid and 3-propenolignan into a mixed solvent of N, N-dimethylformamide and deionized water, slowly adding an ammonium persulfate aqueous solution with the concentration of 25-30wt%, reacting for 2-4 hours at 80-95 ℃, performing rotary evaporation, adding deionized water (the mass volume ratio of the acrylic acid to the deionized water is 1g:25-35 mL), filtering, and drying to obtain the polyacrylic acid derivative.
According to one embodiment of the present invention, the molar ratio of the acrylic acid to 3-propenolignan is: 1:0.7-1.3.
According to one embodiment of the invention, the mass-volume ratio of the acrylic acid to the mixed solvent is as follows: 1g, 30-45mL.
According to one embodiment of the invention, in the mixed solvent, the volume ratio of the N, N-dimethylformamide to the deionized water is as follows: 1:1.5-2.
According to one embodiment of the invention, the mass ratio of acrylic acid to ammonium persulfate is: 1:0.05-0.1.
The invention also discloses the application of the polyacrylic acid derivative prepared by the preparation method in harmless recycling of the waste incineration fly ash.
The invention also discloses the application of the polyacrylic acid derivative prepared by the preparation method in heavy metal ion removal.
The beneficial effects of the invention include:
the invention obtains a harmless recycling method of the waste incineration fly ash, the hazardous waste of the waste incineration fly ash is treated by the method, dioxin is removed from the treated fly ash through low-temperature pyrolysis, and heavy metal is removed through acid washing, so that complete detoxification is realized, the hazardous waste property of the fly ash can be removed through toxicity authentication, and the fly ash and bottom ash enter a building material recycling system together. In addition, the polyacrylic acid derivative is added in the pickling process, so that the heavy metal removal effect is further improved.
Therefore, the invention provides a harmless recycling method of the waste incineration fly ash, which has good removal effect on dioxin and heavy metal ions and realizes recycling of the fly ash.
Drawings
FIG. 1 is a flow chart of a method for harmless recycling of waste incineration fly ash in example 1;
FIG. 2 shows the infrared spectrum of starch derivatives and starches prepared in example 1;
FIG. 3 shows the results of infrared spectrogram test of the polyacrylic acid derivative and polyacrylic acid prepared in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear and clear, the technical solutions of the present invention are described in further detail below with reference to the specific embodiments:
example 1:
a harmless resource utilization method of waste incineration fly ash comprises the following steps:
step one, a certain garbage incineration production line has an incineration amount of 500 t/day and a fly ash generation amount of about 18 t/day, the fly ash is introduced into a hearth in a nitrogen atmosphere, the temperature is kept at 450 ℃, the fly ash is detoxified, and the detoxified gas returns to the incineration hearth;
secondly, pickling the waste incineration fly ash (the mass volume ratio of the fly ash to the pickling solution is 1g:1.5 mL) by using hydrochloric acid pickling solution (the pH value of the pickling solution is 2), wherein the pickling time is 15min; fully mixing and stirring to dissolve heavy metals in the fly ash into acid liquor, and dissolving calcium at the same time;
step three, solid-liquid separation is carried out;
step four, after naturally air-drying the solid phase after solid-liquid separation, adding the solid phase into bottom ash after garbage incineration for building material utilization;
adding sodium sulfate (the mass ratio of fly ash to sodium sulfate is 1:0.3) into the liquid phase after solid-liquid separation, performing solid-liquid separation again, and performing solid-phase drying, crushing and marketing; 90% of the liquid phase returns to the pickling solution, and the residual liquid phase is filtered and discharged out of the system after heavy metals are removed by the heavy metal chelating agent starch derivative. Wherein the treatment time of the heavy metal chelating agent is 60min, and the dosage of the heavy metal chelating agent is 1g/L; the flow chart of the method is shown in fig. 1.
A process for the preparation of a starch derivative comprising the steps of:
adding starch into deionized water, adding an emulsifier OP-10, stirring and mixing uniformly, adding phthalic acid mono-2- (methacryloyloxy) ethyl ester and potassium persulfate, reacting at 55 ℃ for 70min, demulsifying with ethanol, drying, and extracting with acetone to obtain a starch derivative; wherein, the mass volume ratio of the starch to the deionized water is as follows: 1g:25mL; the mass ratio of the starch to the emulsifier is as follows: 1:0.03; the mass ratio of the starch to the mono-2- (methacryloyloxy) ethyl phthalate is as follows: 1:3.5; the concentration of potassium persulfate in the reaction solution was 5.5mmol/L.
Example 2:
the method for harmless recycling of waste incineration fly ash is different from that of the embodiment 1: starch is used instead of starch derivatives.
Example 3:
the method for harmless recycling of waste incineration fly ash is different from that of the embodiment 1: the polyacrylic acid derivative is added into the pickling solution, and the mass ratio of the polyacrylic acid derivative to the hydrochloric acid is as follows: 1:2.
A process for the preparation of polyacrylic acid derivatives comprising the steps of:
adding acrylic acid and 3-propenolignan into a mixed solvent of N, N-dimethylformamide and deionized water, slowly adding an ammonium persulfate aqueous solution with the concentration of 25wt% to react for 4 hours at 80 ℃, performing rotary evaporation, adding deionized water (the mass volume ratio of the acrylic acid to the deionized water is 1g:25 mL), filtering, and drying to obtain the polyacrylic acid derivative. Wherein, the mol ratio of the acrylic acid to the 3-propenolignan is as follows: 1:1; the mass volume ratio of the acrylic acid to the mixed solvent is as follows: 1g:30ml; the mass ratio of the acrylic acid to the ammonium persulfate is as follows: 1:0.05; in the mixed solvent, the volume ratio of the N, N-dimethylformamide to the deionized water is as follows: 1:1.5.
Example 4:
the method for harmless recycling of waste incineration fly ash is different from that of the embodiment 1: polyacrylic acid is added into the pickling solution, and the mass ratio of the polyacrylic acid to the hydrochloric acid is as follows: 1:2.
Example 5:
the method for harmless recycling of waste incineration fly ash is different from that of the embodiment 1: starch derivatives are prepared by different methods.
The process for the preparation of starch derivatives differs from that of example 1: acrylic acid is adopted to replace phthalic acid mono-2- (methacryloyloxy) ethyl ester; the mass ratio of the starch to the acrylic acid is as follows: 1:0.9.
Example 6:
the method for harmless recycling of waste incineration fly ash is different from that of the embodiment 3: the preparation methods of polyacrylic acid derivatives are different.
The process for the preparation of polyacrylic acid derivatives differs from that of example 3: diketene is used instead of 3-propenolignan.
Test example:
1. infrared spectroscopy testing
And (3) adopting a Fourier infrared spectrometer and a potassium bromide tabletting method to analyze and test the sample, wherein the wavelength testing range is as follows: 400-4000cm -1 。
The starch derivatives prepared in example 1 and starch were subjected to the above test, and the results are shown in fig. 2. As can be seen from FIG. 2, the infrared spectrum of the starch derivative is 1400-1600cm -1 There is an infrared characteristic absorption peak of benzene ring at 1711cm -1 There is an infrared characteristic absorption peak of c=o bond, indicating that mono-2- (methacryloyloxy) ethyl phthalate participates in the starch derivative formation reaction.
The polyacrylic acid derivative and polyacrylic acid prepared in example 3 were subjected to the above-described test, and the results are shown in fig. 3. As can be seen from FIG. 3, the polyacrylic acid derivative is compared with the infrared spectrum of polyacrylic acidIs 1066cm in infrared spectrum -1 An infrared characteristic absorption peak of the C-S bond exists at the position; at 1417cm -1 The presence of an infrared characteristic absorption peak of the C-N bond indicates that 3-propenolignan is involved in the formation reaction of polyacrylic acid derivatives.
2. Dioxin removal effect test
2.1 Medium-low temperature pyrolysis test of dioxin removal effect
The detection of dioxin poison is carried out with reference to HJ 77.3-2008, "solid waste dioxin-like assay isotope dilution high resolution gas chromatography-high resolution mass spectrometry".
Table 1 results of low temperature pyrolysis test for dioxin removal effect
| Grouping | Concentration of dioxin (ng-TEQ/kg) |
| Raw fly ash | 650 |
| Fly ash after medium and low temperature pyrolysis | 17 |
The above test was performed on the raw fly ash and the fly ash after middle-low temperature pyrolysis, and the results are shown in table 1. As can be seen from table 1, the medium-low temperature pyrolysis can effectively remove dioxin-like substances in the original fly ash.
2.2 test of the Effect of polyacrylic acid derivatives on removal of dioxins
Detecting dioxin poison by referring to HJ 77.3-2008' high resolution gas chromatography-high resolution mass spectrometry for measuring isotope dilution of solid wastes dioxin; directly introducing the fly ash which is not subjected to medium-temperature pyrolysis treatment into pickling solution, pickling under the pickling condition in the embodiment 1, carrying out solid-liquid separation, naturally air-drying, and carrying out the test on the fly ash; the experimental groupings were as follows: the hydrochloric acid pickling solution is marked as N1; the pickling solution of polyacrylic acid and hydrochloric acid is marked as N2; the pickling solution of polyacrylic acid derivative + hydrochloric acid prepared in example 3 is denoted as N3; the pickling solution of polyacrylic acid derivative + hydrochloric acid prepared in example 6 was designated as N4.
TABLE 2 test results of the effect of pickling on removal of dioxins
| Grouping | Concentration of dioxin (ng-TEQ/kg) |
| Raw fly ash | 650 |
| N1 | 590 |
| N2 | 517 |
| N3 | 435 |
| N4 | 489 |
The above tests were performed on N1-N4 and the results are shown in Table 2. As can be seen from table 2, N1 has a reduced concentration of dioxin compared with the original fly ash, indicating that the use of hydrochloric acid as the pickling solution has a partial removal effect on dioxin in the fly ash; compared with N1, the concentration of the dioxin is also reduced, which indicates that the addition of polyacrylic acid in the pickling solution can further improve the removal effect of the dioxin; compared with N2, the concentration of dioxin is also reduced, which shows that after the 3-propenolignan is adopted to modify polyacrylic acid, the polyacrylic acid derivative is used in pickling solution, so that the method has good effect of removing dioxin in fly ash; the concentration of dioxin is also reduced compared with N4, indicating that the use of 3-propenolignan as a modifier has a better dioxin removal effect than conventional modifiers.
3. Test of removal effect of heavy metal ions in fly ash
The solid phase fly ash sample and the raw fly ash after air drying were tested according to HJT-2007 "method of solid waste leaching toxicity leaching method of acetic acid buffer solution".
TABLE 3 detection results of heavy metal ions in solid-phase fly ash sample after air-drying in EXAMPLE 1
| Analysis index | Method | Unit (B) | Detection limit | Limit value | Detection result |
| Moisture content | HJ 1222 | % | 1 | ＜30 | 16 |
| Hexavalent chromium | GB/T 15555.4 | mg/L | 0.05 | ＜1.5 | ND |
| Barium (Ba) | HJ 781 | mg/L | 0.2 | ＜25 | 1.1 |
| Beryllium (beryllium) | HJ 781 | mg/L | 0.004 | ＜0.02 | ND |
| Cadmium (Cd) | HJ 781 | mg/L | 0.04 | ＜0.15 | ND |
| Chromium (Cr) | HJ 781 | mg/L | 0.08 | ＜4.5 | ND |
| Copper (Cu) | HJ 781 | mg/L | 0.04 | ＜40 | ND |
| Nickel (Ni) | HJ 781 | mg/L | 0.08 | ＜0.5 | ND |
| Lead | HJ 781 | mg/L | 0.12 | ＜0.25 | ND |
| Zinc alloy | HJ 781 | mg/L | 0.04 | ＜100 | ND |
| Arsenic (As) | HJ 702 | mg/L | 0.0001 | ＜0.3 | 0.0015 |
| Mercury | HJ 702 | mg/L | 2×10 -5 | ＜0.05 | 0.00041 |
| Selenium (Se) | HJ 702 | mg/L | 0.0001 | ＜0.1 | 0.0008 |
TABLE 4 test results of heavy metal ion removal effect
| Grouping | Barium ion concentration (mg/L) | Calcium ion concentration (mg/L) |
| Raw fly ash | 23 | 7115 |
| Example 1 | 1.1 | 29 |
| Example 3 | 0.3 | 12 |
| Example 4 | 0.6 | 18 |
| Example 6 | 0.5 | 16 |
The above test was performed on the raw fly ash and the solid-phase fly ash sample after air drying, and the results are shown in Table 4. As is clear from Table 4, in example 1, the concentration of barium ions and the concentration of calcium ions were significantly reduced as compared with the original fly ash, which indicates that the hydrochloric acid pickling solution has a good eluting effect on heavy metal ions in the fly ash; example 4 also shows a significant reduction in barium ion concentration and calcium ion concentration compared to example 1, indicating that the addition of polyacrylic acid to the pickling solution facilitates the further removal of heavy metal ions from the fly ash; example 3 also showed a decrease in barium ion concentration and calcium ion concentration compared with example 4, demonstrating that the use of the polyacrylic acid derivative in the pickling solution after the use of the 3-propenolignan modified polyacrylic acid has a better elution effect on heavy metal ions in fly ash; example 4 also showed a decrease in the barium ion concentration and the calcium ion concentration as compared with example 6, indicating that the use of 3-propenolignan as a modifier has a superior heavy metal ion removal effect as compared with the conventional modifier.
4. Test of heavy metal ion removal effect of heavy metal chelating agent
Measuring the concentration of barium ions in the liquid before and after the treatment of the heavy metal chelating agent by using an atomic absorption spectrometry; the calculation formula of the heavy metal ion removal rate is as follows:
E/%=[(K0-K1)/K0]×100%
wherein E is the heavy metal ion removal rate; k0 is the concentration of heavy metal ions before treatment with the heavy metal chelating agent; k1 is the concentration of heavy metal ions after treatment of heavy metal chelating agents.
TABLE 5 test results of heavy metal ion removal effect of heavy metal chelating agent
| Grouping | Heavy metal ion removal rate/% |
| Example 1 | 86.9 |
| Example 2 | 75.3 |
| Example 5 | 81.7 |
The above-described test was performed on the liquids before and after the treatment with the heavy metal chelating agent in example 1 and example 2, and the results are shown in table 5. As can be seen from table 3, the removal rate of heavy metal ions is significantly improved in example 2 compared with example 1, which indicates that the starch derivative prepared by using mono-2- (methacryloyloxy) ethyl phthalate has good removal effect on heavy metal ions when used as a heavy metal chelating agent; example 1 also showed an improvement in the removal rate of heavy metal ions as compared with example 5, indicating that the use of mono-2- (methacryloyloxy) ethyl phthalate as a modifier has a superior effect of removing heavy metal ions as compared with conventional modifiers.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A harmless resource utilization method of waste incineration fly ash comprises the following steps:
step one, pyrolyzing fly ash at low temperature;
step two, pickling is carried out by using pickling solution;
step three, solid-liquid separation;
step four, recycling the solid phase;
adding sodium sulfate into the liquid phase, separating solid from liquid, recycling 85-95% of acid liquor, removing heavy metals from the residual acid liquor by a heavy metal chelating agent, and discharging the residual acid liquor out of the system;
the temperature of the medium-low temperature pyrolysis is 400-500 ℃;
the pH value of the pickling solution is less than 2.64;
the heavy metal chelating agent comprises a starch derivative;
the preparation method of the starch derivative comprises the following steps: adding starch into deionized water, adding an emulsifying agent, stirring and mixing uniformly, adding mono-2- (methacryloyloxy) ethyl phthalate and potassium persulfate, reacting at 55-70 ℃ for 40-70min, demulsifying with ethanol, drying, and extracting with acetone to obtain starch derivative.
2. The method for harmless recycling of waste incineration fly ash according to claim 1, which is characterized in that: the pickling solution contains hydrochloric acid.
3. The method for harmless recycling of waste incineration fly ash according to claim 1, which is characterized in that: the mass volume ratio of the fly ash to the pickling solution is as follows: 1g, 1.4-2mL.
4. The method for harmless recycling of waste incineration fly ash according to claim 1, which is characterized in that: the pickling time is 10-20min.
5. The method for harmless recycling of waste incineration fly ash according to claim 1, which is characterized in that: adding polyacrylic acid derivatives into the pickling solution; the preparation method of the polyacrylic acid derivative comprises the following steps: the polyacrylic acid derivative is prepared by adopting 3-propenylrhodanine to carry out grafting reaction with acrylic acid.
6. The use of the starch derivative according to claim 1 in the harmless recycling of waste incineration fly ash.
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