CN118127315A - Method for recycling high-grade composite heavy metal material and product thereof - Google Patents
Method for recycling high-grade composite heavy metal material and product thereof Download PDFInfo
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 137
- 239000007769 metal material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000004064 recycling Methods 0.000 title claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 92
- 239000002893 slag Substances 0.000 claims abstract description 89
- 239000010802 sludge Substances 0.000 claims abstract description 75
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 73
- 239000001301 oxygen Substances 0.000 claims abstract description 73
- 238000007639 printing Methods 0.000 claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 53
- 238000004056 waste incineration Methods 0.000 claims abstract description 49
- 239000010881 fly ash Substances 0.000 claims abstract description 48
- 238000004043 dyeing Methods 0.000 claims abstract description 47
- 230000008569 process Effects 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000227 grinding Methods 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003546 flue gas Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 10
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 239000002910 solid waste Substances 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 26
- 239000002956 ash Substances 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910001504 inorganic chloride Inorganic materials 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052790 beryllium Inorganic materials 0.000 description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052716 thallium Inorganic materials 0.000 description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a method for recycling high-grade composite heavy metal materials and a product thereof, wherein the method comprises the following steps: mixing printing and dyeing sludge, waste incineration fly ash and lithium slag powder, granulating, calcining, and recovering flue gas generated in the calcining process to obtain heavy metal enriched coarse material; mixing with printing and dyeing sludge, granulating, calcining with oxygen enrichment, grinding the residue into powder, mixing with water, and drying the solid obtained after solid-liquid separation to obtain the high-grade composite heavy metal material. The preparation method is simple, the required raw materials are solid wastes, the waste incineration fly ash, lithium slag and printing and dyeing sludge are cooperatively treated, the effective recovery of heavy metal pollutants in the waste incineration fly ash, lithium slag and printing and dyeing sludge is realized through reasonable proportioning and combined calcination and oxygen-enriched calcination processes, the total metal content of the prepared composite heavy metal material is up to 42 percent (calculated by oxide), and the high-efficient recovery of heavy metal resources from dangerous solid wastes is truly realized.
Description
Technical Field
The invention relates to a method for recycling high-grade composite heavy metal materials and a product thereof, belonging to the field of recycling of dangerous wastes.
Background
Waste incineration fly ash and lithium slag are two typical solid wastes generated in the industrial production and municipal solid waste treatment processes. Along with the acceleration of the urban process and the improvement of the industrialization degree, the garbage treatment and the recycling of the solid wastes become an important issue in the current environmental protection field. Waste incineration is an effective way of disposing of waste, and the fly ash produced by the waste incineration contains a certain amount of heavy metal pollutants, which constitutes a potential threat to the environment. The waste incineration fly ash is a residue left after the organic matters in the waste are combusted under the high temperature condition. These residues contain heavy metal pollutants such as lead, cadmium, zinc, copper and the like, have toxicity and bioaccumulation, and if the residues are directly discharged or utilized without treatment, the residues pollute soil, water bodies and ecosystems, and threaten human health.
The lithium slag mainly originates from the processing process of lithium ores and the process of producing lithium carbonate by using a sulfuric acid method, contains compounds such as silicate, carbonate, sulfate and the like, and contains a certain proportion of lithium elements and other heavy metal components. The appearance of the lithium slag is generally earthy yellow, and the lithium slag is powdery after being dried, has small particles and has certain cohesive force. In the fields of building materials, chemical industry and the like, the lithium slag can be used as a mineral admixture after being treated to a certain extent. The lithium slag is industrial waste slag, and through reasonable treatment and utilization, the problems of waste slag discharge and environmental pollution can be solved, the recycling of resources can be realized, and the sustainable development is promoted.
The recycling of resources can be realized by cooperatively recycling heavy metals in the waste incineration fly ash and the lithium slag, and the exploitation requirement on new resources is reduced. Meanwhile, the release of heavy metals in the environment can be reduced by effectively recycling the heavy metals, the pollution risk to soil, water and an ecological system is reduced, the green transformation of economy is promoted, and the development of circular economy is promoted. Aiming at the research of the problem of heavy metal pollution in the waste incineration fly ash and lithium slag and exploring the theoretical feasibility and environmental advantages of the cooperative recovery of the waste incineration fly ash and the lithium slag, the method has important significance for promoting the progress of environmental protection technology and realizing sustainable development.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a method for recycling high-grade composite heavy metal materials by cooperatively utilizing waste incineration fly ash and lithium slag, which has the advantages of simple preparation method and capability of realizing effective recycling of heavy metal pollutants, and a product thereof.
The technical scheme is as follows: in order to solve the technical problems, the invention provides a method for recycling high-grade composite heavy metal materials by cooperatively utilizing waste incineration fly ash and lithium slag, which comprises the following steps:
(1) Mixing the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder, uniformly stirring, granulating, calcining, and recovering the flue gas generated in the calcining process through a cooling pipeline and a spiral separator to obtain heavy metal enriched coarse materials;
(2) Mixing the printing and dyeing sludge and the heavy metal enriched coarse material in the step (1), stirring, granulating, and performing oxygen-enriched calcination to obtain residue which is oxygen-enriched calcined residue;
(3) Grinding the oxygen-enriched calcined slag in the step (2) into powder, mixing water and the oxygen-enriched calcined slag powder, stirring, and carrying out solid-liquid separation to obtain a solid part, and drying the solid part to obtain the high-grade composite heavy metal material.
Wherein, in the step (1), the lithium slag powder is 200-800 meshes.
The mass ratio of the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder in the step (1) is 20-60:30-120:100, and the total heavy metal content of the prepared composite heavy metal material is higher than 33%.
Wherein the calcining temperature in the step (1) is 700-1100 ℃ and the calcining time is 0.5-5.5 hours.
The mass ratio of the printing and dyeing sludge to the heavy metal enriched coarse material in the step (2) is 5-25:100, and the total heavy metal content of the prepared composite heavy metal material is higher than 37%.
Wherein the temperature of the oxygen-enriched calcination in the step (2) is 900-1200 ℃, and the oxygen content is 25-45%.
Wherein the time of oxygen-enriched calcination in the step (2) is 1-5 hours, and the total heavy metal content of the prepared composite heavy metal material is higher than 41%.
Wherein in the step (3), the liquid-solid ratio of the water to the oxygen-enriched calcined slag powder is 3-12:1 mL/g.
Wherein the stirring time in the step (3) is 0.5-2.5 hours.
The invention also provides a high-grade composite heavy metal material prepared by the method.
Reaction mechanism: mixing the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder, dissolving and penetrating the soluble chloride salt in the waste incineration fly ash into the printing and dyeing sludge and the lithium slag powder in the stirring and granulating processes, and penetrating and adsorbing the organic substances in the printing and dyeing sludge into the surfaces and pores of the particles of the waste incineration fly ash and the lithium slag powder under the action of electrostatic adsorption and pore adsorption. Calcining the ash mud particles, wherein inorganic chloride in the waste incineration fly ash is used as a catalyst in the calcining process to promote the pyrolysis reaction and the oxidation combustion reaction of organic matters in the printing and dyeing sludge to generate micromolecular gas and solid carbon black, and part of the gas and the solid carbon black further undergo the oxidation combustion reaction at high temperature to generate carbon dioxide and water vapor. Inorganic chloride in the waste incineration fly ash reacts with beryllium, thallium in the zinc, lead, copper, cadmium and lithium slag powder carried by the inorganic chloride on the surface of the carbon black and a small amount of heavy metal pollutants carried by the dye printing sludge to generate heavy metal chloride, the boiling point of the heavy metal chloride is reduced under the action of carbothermal chlorination, the saturated vapor pressure is increased, the heavy metal chloride, along with unreacted carbon black, other volatile chloride and other burning-loss components, enters the atmosphere, and is recovered in a flue gas through a cooling pipeline and a spiral separator to obtain heavy metal enriched coarse material. Mixing the printing and dyeing sludge and the heavy metal enriched coarse material, and penetrating the soluble inorganic salt and the organic pollutant in the printing and dyeing sludge into the heavy metal enriched coarse material. The coarse material mud particles are subjected to oxygen-enriched calcination, the combustion efficiency of the printing and dyeing sludge is improved by increasing the proportion of oxygen in the combustion process, a large amount of alkaline ash is generated, carbon thermal chlorination is avoided, and the formation and re-release of low-boiling ferric chloride and aluminum chloride are promoted, so that the taste of heavy metal materials is further improved. And in the oxygen-enriched calcination process, alkaline ash generated by the oxidation reaction of the printing and dyeing sludge is melted and wraps heavy metal, so that the alkaline ash is promoted to be combined with and oxidized by the heavy metal, and a heavy metal mineral phase with stable crystalline phase is formed. Mixing water and oxygen-enriched calcined slag powder according to a liquid-solid ratio, and dissolving soluble salt and unreacted ash in the oxygen-enriched calcined slag powder into the water in the stirring process, so as to further improve the heavy metal taste in the enriched aggregate.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the preparation method is simple, the required raw materials are solid wastes, the waste incineration fly ash, lithium slag and printing and dyeing sludge are cooperatively treated, the effective recovery of heavy metal pollutants in the waste incineration fly ash, lithium slag and printing and dyeing sludge is realized through reasonable proportioning and combined calcination and oxygen-enriched calcination processes, the total metal content of the prepared composite heavy metal material is up to 42 percent (calculated by oxide), and the high-efficient recovery of heavy metal resources from dangerous solid wastes is truly realized.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Printing and dyeing sludge: the printing and dyeing sludge is provided by Shaoxing Ke Qiao Yu printing and dyeing limited company, and the chemical components mainly comprise 43.86% SO 3、36.34%Fe2O3、7.01%SiO2、5.82%Al2O3, 2.93% CaO and other components (loss on ignition and other unavoidable impurities);
Waste incineration fly ash: the waste incineration fly ash is provided by a second household waste incineration power plant which is normally mature in Jiangsu, mainly comprises 38.14%CaO、24.05%Cl、10.21%SO3、12.15%Na2O、6.21%K2O、3.17%SiO2、1.41%Fe2O3、1.19%Al2O3 and other components (loss on ignition and other unavoidable impurities), wherein the content of zinc in the other components is 0.43 percent (calculated by ZnO), the content of lead in the other components is 0.14 percent (calculated by PbO), the content of copper in the other components is 0.31 percent (calculated by CuO), and the content of cadmium in the other components is 0.09 percent (calculated by CdO);
Lithium slag: the lithium slag is from a new energy industry base of Yichun lithium battery, and the main chemical components comprise ：57.94%SiO2、24.57%Al2O3、6.15%CaO、7.24%SO3、0.45%K2O、0.62%Na2O、0.21%MgO、1.23%Fe2O3 and other components (unavoidable impurities and loss on ignition), wherein the thallium content in the other components is 0.12% (calculated by Tl 2O3) and the beryllium content is 0.08% (calculated by BeO).
Example 1 influence of the mass ratio of printing sludge, waste incineration fly ash and lithium slag powder on the grade of the heavy metal material prepared
Grinding the lithium slag, and sieving the ground lithium slag with a 200-mesh sieve to obtain lithium slag powder. Mixing the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder according to the mass ratio 12.5:30:100、15:30:100、17.5:30:100、20:22.5:100、20:25:100、20:27.5:100、20:30:100、40:30:100、60:30:100、20:75:100、40:75:100、60:75:100、20:120:100、40:120:100、60:120:100、60:130:100、60:140:100、60:150:100、65:120:100、70:120:100、75:120:100, uniformly stirring, adding a proper amount of water, and granulating to obtain ash and sludge particles. And (3) calcining the ash mud particles, wherein the flue gas generated in the calcining process is recovered through a cooling pipeline and a spiral separator to obtain heavy metal enriched coarse material, and the calcining temperature is 700 ℃ and the calcining time is 0.5 hour. Mixing the printing and dyeing sludge and heavy metal enriched coarse material according to the mass ratio of 5:100, uniformly stirring, adding a proper amount of water, and granulating to obtain coarse material mud particles. And (3) carrying out oxygen-enriched calcination on the coarse material mud particles to obtain residue which is oxygen-enriched calcination residue, wherein the calcination temperature is 900 ℃, the calcination time is 1 hour, and the oxygen content is 25%. Grinding the oxygen-enriched calcined slag into powder, mixing water and the oxygen-enriched calcined slag powder according to a liquid-solid ratio of 3:1mL/g, stirring for 0.5 hour, and carrying out solid-liquid separation to obtain a solid part, and drying the solid part to obtain the high-grade composite heavy metal material.
And detecting the total heavy metal content of the composite heavy metal material: and carrying out X-ray fluorescence spectrum analysis on the prepared composite heavy metal material, and counting the sum (calculated by oxide) of the contents of heavy metals zinc, lead, copper, cadmium, beryllium and thallium. The test results of this example are shown in Table 1.
TABLE 1 influence of mass ratio of printing and dyeing sludge, waste incineration fly ash and lithium slag powder on grade of heavy metal materials prepared
As can be seen from table 1, when the mass ratio of the printing sludge, the waste incineration fly ash, and the lithium slag powder is less than 20:30:100 (as in table 1, the printing sludge, the waste incineration fly ash, and the lithium slag powder mass ratio=17.5:30:100, 15:30:100, 12.5:30:100, 20:27.5:100, 20:25:100, and 20:22.5:100, and the lower ratio not listed in table 1), the printing sludge and the waste incineration fly ash are added less, and the printing sludge, the waste incineration fly ash, and the lithium slag are not reacted sufficiently during the calcination, resulting in that the total heavy metal content of the prepared heavy metal material follows the printing sludge, The mass ratio of the waste incineration fly ash to the lithium slag powder is reduced to be obviously reduced. When the mass ratio of the printing sludge, the waste incineration fly ash and the lithium slag powder is equal to 20-60:30-120:100 (as in table 1, the mass ratio of the printing sludge, the waste incineration fly ash and the lithium slag powder=20:30:100, 40:30:100, 60:30:100, 20:75:100, 40:75:100, 60:75:100, 20:120:100, 40:120:100 and 60:120:100), the soluble chloride in the waste incineration fly ash is dissolved and permeated into the printing sludge and the lithium slag powder in the stirring and granulating process, and organic substances in the printing and dyeing sludge permeate and are adsorbed on the surfaces and pores of the garbage incineration fly ash and lithium slag powder particles under the action of electrostatic adsorption and pore adsorption. Calcining the ash mud particles, wherein inorganic chloride in the waste incineration fly ash is used as a catalyst in the calcining process to promote the pyrolysis reaction and the oxidation combustion reaction of organic matters in the printing and dyeing sludge to generate micromolecular gas and solid carbon black, and part of the gas and the solid carbon black further undergo the oxidation combustion reaction at high temperature to generate carbon dioxide and water vapor. Inorganic chloride in the waste incineration fly ash reacts with beryllium, thallium in the zinc, lead, copper, cadmium and lithium slag powder carried by the inorganic chloride on the surface of the carbon black and a small amount of heavy metal pollutants carried by the dye printing sludge to generate heavy metal chloride, the boiling point of the heavy metal chloride is reduced under the action of carbothermal chlorination, the saturated vapor pressure is increased, the heavy metal chloride, along with unreacted carbon black, other volatile chloride and other burning-loss components, enters the atmosphere, and is recovered in a flue gas through a cooling pipeline and a spiral separator to obtain heavy metal enriched coarse material. Finally, the total content of heavy metals in the prepared composite heavy metal material is higher than 33%. When the mass ratio of the printing sludge, the waste incineration fly ash and the lithium slag powder is greater than 60:120:100 (as in table 1, the mass ratio of the printing sludge, the waste incineration fly ash and the lithium slag powder=60:130:100, 60:140:100, 60:150:100, 65:120:100, 70:120:100, 75:120:100 and higher ratios not listed in table 1), the printing sludge and the waste incineration fly ash are excessively added, the material reaction is unbalanced in the calcination process, and the total heavy metal content of the prepared heavy metal material is obviously reduced as the mass ratio of the printing sludge, the waste incineration fly ash and the lithium slag powder is further increased.
Therefore, when the mass ratio of the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder is equal to 20-60:30-120:100, the total heavy metal content of the prepared composite heavy metal material is most favorable for improvement.
Example 2 influence of the quality ratio of printing and dyeing sludge and heavy Metal enriched coarse Material on the grade of the heavy Metal Material produced
Grinding the lithium slag, and sieving with a 500-mesh sieve to obtain lithium slag powder. Mixing the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder according to the mass ratio of 60:120:100, uniformly stirring, adding a proper amount of water, and granulating to obtain ash and sludge granules. And (3) calcining the ash mud particles, wherein the flue gas generated in the calcining process is recovered through a cooling pipeline and a spiral separator to obtain heavy metal enriched coarse material, and the calcining temperature is 900 ℃ and the calcining time is 3 hours. Mixing the printing and dyeing sludge and heavy metal enriched coarse material according to the mass ratio of 2.5:100, 3:100, 4:100, 5:100, 15:100, 25:100, 27.5:100, 30:100 and 32.5:100, uniformly stirring, adding a proper amount of water, and granulating to obtain coarse material mud particles. And (3) carrying out oxygen-enriched calcination on the coarse material mud particles to obtain residue which is oxygen-enriched calcination residue, wherein the calcination temperature is 1050 ℃, the calcination time is 3 hours, and the oxygen content is 35%. Grinding the oxygen-enriched calcined slag into powder, mixing water and the oxygen-enriched calcined slag powder according to a liquid-solid ratio of 7.5:1mL/g, stirring for 1.5 hours, and carrying out solid-liquid separation to obtain a solid part, and drying the solid part to obtain the high-grade composite heavy metal material.
The total content of heavy metals in the composite heavy metal material is detected in the same way as in example 1, and the test results of this example are shown in Table 2.
TABLE 2 influence of the mass ratio of printing sludge to heavy metal enriched coarse material on the grade of the heavy metal material produced
As can be seen from table 2, when the mass ratio of the printing sludge to the heavy metal enriched coarse material is less than 20:30:100 (as in table 2, when the mass ratio of the printing sludge to the heavy metal enriched coarse material=4:100, 3:100, 2.5:100 and lower ratio not listed in table 2), the printing sludge is added less, the amount of alkaline ash generated during the oxygen-enriched calcination is reduced, resulting in a significant reduction in the total heavy metal content of the prepared heavy metal material as the mass ratio of the printing sludge to the heavy metal enriched coarse material is reduced. When the mass ratio of the printing and dyeing sludge to the heavy metal enriched coarse material is equal to 5-25:100 (as in table 2, when the mass ratio of the printing and dyeing sludge to the heavy metal enriched coarse material=5:100, 15:100, 25:100), mixing the printing and dyeing sludge and the heavy metal enriched coarse material, wherein the soluble inorganic salt and the organic pollutant in the printing and dyeing sludge permeate into the heavy metal enriched coarse material. Finally, the total content of heavy metals in the prepared composite heavy metal material is higher than 37%. When the mass ratio of the printing sludge to the heavy metal enriched coarse material is greater than 25:100 (as in table 2, the mass ratio of the printing sludge to the heavy metal enriched coarse material=27.5:100, 30:100, 32.5:100 and higher ratios not listed in table 2), the printing sludge is excessively added, the material reaction is unbalanced in the oxygen-enriched calcination process, and the total heavy metal content of the prepared heavy metal material is significantly reduced as the mass ratio of the printing sludge to the heavy metal enriched coarse material is further increased.
Therefore, when the mass ratio of the printing and dyeing sludge to the heavy metal enriched coarse material is equal to 5-25:100, the total heavy metal content of the prepared composite heavy metal material is improved most favorably.
Example 3 influence of oxygen-enriched calcination time on grade of heavy metal material produced
Grinding the lithium slag, and sieving the ground lithium slag with a 800-mesh sieve to obtain lithium slag powder. Mixing the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder according to the mass ratio of 60:120:100, uniformly stirring, adding a proper amount of water, and granulating to obtain ash and sludge granules. And (3) calcining the ash mud particles, wherein the flue gas generated in the calcining process is recovered through a cooling pipeline and a spiral separator to obtain heavy metal enriched coarse material, and the calcining temperature is 1100 ℃ and the calcining time is 5.5 hours. Mixing the printing and dyeing sludge and heavy metal enriched coarse material according to the mass ratio of 25:100, uniformly stirring, adding a proper amount of water, and granulating to obtain coarse material mud particles. And (3) carrying out oxygen-enriched calcination on the coarse material mud particles to obtain residues which are oxygen-enriched calcined residues, wherein the calcination temperature is 1200 ℃, the calcination time is 0.5 hour, 0.6 hour, 0.8 hour, 1 hour, 3 hours, 5 hours, 5.5 hours, 6 hours and 6.5 hours, and the oxygen content is 45%. Grinding the oxygen-enriched calcined slag into powder, mixing water and the oxygen-enriched calcined slag powder according to a liquid-solid ratio of 12:1mL/g, stirring for 2.5 hours, and carrying out solid-liquid separation to obtain a solid part, and drying the solid part to obtain the high-grade composite heavy metal material.
The total content of heavy metals in the composite heavy metal material is detected in the same way as in example 1, and the test results of this example are shown in Table 3.
TABLE 3 influence of oxygen-enriched calcination time on grade of heavy metal materials produced
As can be seen from table 3, when the oxygen-enriched calcination time is less than 1 hour (as in table 3, oxygen-enriched calcination time=0.8 hour, 0.6 hour, 0.5 hour, and lower values not listed in table 3), the oxygen-enriched calcination time is short, the reaction between the materials during the oxygen-enriched calcination is insufficient, resulting in a significant decrease in the total heavy metal content of the heavy metal material produced as the oxygen-enriched calcination time decreases. When the oxygen-enriched calcination time is equal to 1-5 hours (as in table 3, the oxygen-enriched calcination time=1 hour, 3 hours and 5 hours), the coarse material mud particles are subjected to oxygen-enriched calcination, the combustion efficiency of the printing and dyeing sludge is improved by increasing the proportion of oxygen in the combustion process, a large amount of alkaline ash is generated, and simultaneously, the occurrence of carbon thermal chlorination is avoided, and the formation and re-release of low-boiling ferric chloride and aluminum chloride are promoted, so that the taste of heavy metal materials is further improved. And in the oxygen-enriched calcination process, alkaline ash generated by the oxidation reaction of the printing and dyeing sludge is melted and wraps heavy metal, so that the alkaline ash is promoted to be combined with and oxidized by the heavy metal, and a heavy metal mineral phase with stable crystalline phase is formed. . Finally, the total content of heavy metals in the prepared composite heavy metal material is higher than 41%. When the oxygen-enriched calcination time is more than 5 hours (as in table 3, oxygen-enriched calcination time=5.5 hours, 6 hours, 6.5 hours, and higher values not listed in table 3), the oxygen-enriched calcination time is too long, and the material is over-calcined, resulting in a significant decrease in the total heavy metal content of the prepared heavy metal material as the oxygen-enriched calcination time is further increased.
Therefore, in combination, the benefits and the cost are combined, and when the oxygen-enriched calcination time is equal to 1-5 hours, the total heavy metal content of the prepared composite heavy metal material is improved most favorably.
Comparative examples influence of different processes on grade of heavy metal materials prepared
The process comprises the following steps: grinding the lithium slag, and sieving the ground lithium slag with a 800-mesh sieve to obtain lithium slag powder. Mixing the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder according to the mass ratio of 60:120:100, uniformly stirring, adding a proper amount of water, and granulating to obtain ash and sludge granules. And (3) calcining the ash mud particles, wherein the flue gas generated in the calcining process is recovered through a cooling pipeline and a spiral separator to obtain heavy metal enriched coarse material, and the calcining temperature is 1100 ℃ and the calcining time is 5.5 hours. Mixing the printing and dyeing sludge and heavy metal enriched coarse material according to the mass ratio of 25:100, uniformly stirring, adding a proper amount of water, and granulating to obtain coarse material mud particles. And (3) carrying out oxygen-enriched calcination on the coarse material mud particles to obtain residue which is oxygen-enriched calcination residue, wherein the calcination temperature is 1200 ℃, the calcination time is 5 hours, and the oxygen content is 45%. Grinding the oxygen-enriched calcined slag into powder, mixing water and the oxygen-enriched calcined slag powder according to a liquid-solid ratio of 12:1mL/g, stirring for 2.5 hours, and carrying out solid-liquid separation to obtain a solid part, and drying the solid part to obtain the high-grade composite heavy metal material.
Comparison Process 1: grinding the lithium slag, and sieving the ground lithium slag with a 800-mesh sieve to obtain lithium slag powder. Mixing the waste incineration fly ash and the lithium slag powder according to the mass ratio of 120:100, uniformly stirring, adding a proper amount of water, and granulating to obtain ash slag particles. And (3) calcining the ash particles, and recovering flue gas generated in the calcining process through a cooling pipeline and a spiral separator to obtain heavy metal enriched coarse material, wherein the calcining temperature is 1100 ℃, and the calcining time is 5.5 hours. Mixing the printing and dyeing sludge and heavy metal enriched coarse material according to the mass ratio of 25:100, uniformly stirring, adding a proper amount of water, and granulating to obtain coarse material mud particles. And (3) carrying out oxygen-enriched calcination on the coarse material mud particles to obtain residue which is oxygen-enriched calcination residue, wherein the calcination temperature is 1200 ℃, the calcination time is 5 hours, and the oxygen content is 45%. Grinding the oxygen-enriched calcined slag into powder, mixing water and the oxygen-enriched calcined slag powder according to a liquid-solid ratio of 12:1mL/g, stirring for 2.5 hours, and carrying out solid-liquid separation to obtain a solid part, and drying the solid part to obtain the high-grade composite heavy metal material.
Comparison process 2: grinding the lithium slag, and sieving the ground lithium slag with a 800-mesh sieve to obtain lithium slag powder. Mixing the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder according to the mass ratio of 60:120:100, uniformly stirring, adding a proper amount of water, and granulating to obtain ash and sludge granules. And (3) calcining the ash mud particles, wherein the flue gas generated in the calcining process is recovered through a cooling pipeline and a spiral separator to obtain heavy metal enriched coarse material, and the calcining temperature is 1100 ℃ and the calcining time is 5.5 hours. Adding a proper amount of water into the heavy metal enriched coarse material for granulation to obtain coarse material particles. And (3) carrying out oxygen-enriched calcination on the coarse grains to obtain residues which are oxygen-enriched calcined residues, wherein the calcination temperature is 1200 ℃, the calcination time is 5 hours, and the oxygen content is 45%. Grinding the oxygen-enriched calcined slag into powder, mixing water and the oxygen-enriched calcined slag powder according to a liquid-solid ratio of 12:1mL/g, stirring for 2.5 hours, and carrying out solid-liquid separation to obtain a solid part, and drying the solid part to obtain the high-grade composite heavy metal material.
The total content of heavy metals in the composite heavy metal material is detected in the same way as in example 1, and the test results of this example are shown in Table 4.
TABLE 4 influence of different technologies on grade of heavy metal materials prepared
As can be seen from Table 4, the heavy metal material content prepared by the process of the present invention is significantly higher than that of comparative process 1 and comparative process 2, and the heavy metal material content prepared by the process of the present invention is higher than the sum of the heavy metal contents of the heavy metal materials prepared by comparative process 1 and comparative process 2.
Claims (10)
1. The method for recycling the high-grade composite heavy metal material is characterized by comprising the following steps of:
(1) Mixing the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder, uniformly stirring, granulating, calcining, and recovering the flue gas generated in the calcining process through a cooling pipeline and a spiral separator to obtain heavy metal enriched coarse materials;
(2) Mixing the printing and dyeing sludge and the heavy metal enriched coarse material in the step (1), stirring, granulating, and performing oxygen-enriched calcination to obtain residue which is oxygen-enriched calcined residue;
(3) Grinding the oxygen-enriched calcined slag in the step (2) into powder, mixing water and the oxygen-enriched calcined slag powder, stirring, and carrying out solid-liquid separation to obtain a solid part, and drying the solid part to obtain the high-grade composite heavy metal material.
2. The method of claim 1, wherein the lithium slag powder in step (1) is 200-800 mesh.
3. The method according to claim 1, wherein the mass ratio of the printing and dyeing sludge, the waste incineration fly ash and the lithium slag powder in the step (1) is 20-60:30-120:100.
4. The method of claim 1, wherein the calcination in step (1) is performed at a temperature of 700 to 1100 ℃ for a time of 0.5 to 5.5 hours.
5. The method according to claim 1, wherein the mass ratio of the printing and dyeing sludge to the heavy metal enriched coarse material in the step (2) is 5-25:100.
6. The method of claim 1, wherein the oxygen-enriched calcination in step (2) is performed at a temperature of 900-1200 ℃ and an oxygen content of 25-45%.
7. The method of claim 1, wherein the time of the oxygen-enriched calcination in step (2) is 1 to 5 hours.
8. The method of claim 1, wherein in the step (3), the liquid-solid ratio of the water to the oxygen-enriched calcined slag powder is 3-12:1 ml/g.
9. The method of claim 1, wherein the stirring time in step (3) is 0.5 to 2.5 hours.
10. A high grade composite heavy metal material prepared by the method of any one of claims 1 to 9.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003039046A (en) * | 2001-07-31 | 2003-02-12 | Mitsubishi Materials Corp | Method and apparatus for treating fly ash or the like |
| CN104070054A (en) * | 2014-07-02 | 2014-10-01 | 天津壹鸣环境工程有限公司 | Waste incineration fly ash sintering reduction treatment technique |
| CN113620548A (en) * | 2021-07-22 | 2021-11-09 | 江苏荣信环保科技有限公司 | Harmless recycling treatment process method for sludge containing various different heavy metals |
| CN116462429A (en) * | 2023-06-20 | 2023-07-21 | 常熟理工学院 | Method for preparing cementing material by cooperatively disposing waste incineration fly ash and manganese slag |
| CN116553541A (en) * | 2023-04-27 | 2023-08-08 | 常熟理工学院 | Method for preparing activated carbon and cementing material by cooperatively utilizing waste incineration fly ash and oil sludge |
| CN117123591A (en) * | 2023-10-26 | 2023-11-28 | 常熟理工学院 | Method for dry dechlorination of waste incineration fly ash and synchronous preparation of liquid chlorine and solidified soil |
| CN117735573A (en) * | 2023-12-19 | 2024-03-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Treatment method of fused salt chlorination dust collection slag |
-
2024
- 2024-05-08 CN CN202410560002.XA patent/CN118127315A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003039046A (en) * | 2001-07-31 | 2003-02-12 | Mitsubishi Materials Corp | Method and apparatus for treating fly ash or the like |
| CN104070054A (en) * | 2014-07-02 | 2014-10-01 | 天津壹鸣环境工程有限公司 | Waste incineration fly ash sintering reduction treatment technique |
| CN113620548A (en) * | 2021-07-22 | 2021-11-09 | 江苏荣信环保科技有限公司 | Harmless recycling treatment process method for sludge containing various different heavy metals |
| CN116553541A (en) * | 2023-04-27 | 2023-08-08 | 常熟理工学院 | Method for preparing activated carbon and cementing material by cooperatively utilizing waste incineration fly ash and oil sludge |
| CN116462429A (en) * | 2023-06-20 | 2023-07-21 | 常熟理工学院 | Method for preparing cementing material by cooperatively disposing waste incineration fly ash and manganese slag |
| CN117123591A (en) * | 2023-10-26 | 2023-11-28 | 常熟理工学院 | Method for dry dechlorination of waste incineration fly ash and synchronous preparation of liquid chlorine and solidified soil |
| CN117735573A (en) * | 2023-12-19 | 2024-03-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Treatment method of fused salt chlorination dust collection slag |
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