CN114700354A - Harmless treatment method for industrial waste salt - Google Patents
Harmless treatment method for industrial waste salt Download PDFInfo
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- CN114700354A CN114700354A CN202210434295.8A CN202210434295A CN114700354A CN 114700354 A CN114700354 A CN 114700354A CN 202210434295 A CN202210434295 A CN 202210434295A CN 114700354 A CN114700354 A CN 114700354A
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- Prior art keywords
- industrial waste
- waste salt
- salt
- harmless treatment
- solid solution
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- 150000003839 salts Chemical class 0.000 title claims abstract description 92
- 239000002440 industrial waste Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000006104 solid solution Substances 0.000 claims abstract description 20
- -1 alkali metal salt Chemical class 0.000 claims abstract description 18
- 238000010791 quenching Methods 0.000 claims abstract description 18
- 230000000171 quenching effect Effects 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 231100000331 toxic Toxicity 0.000 claims abstract description 6
- 230000002588 toxic effect Effects 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 230000003628 erosive effect Effects 0.000 claims abstract description 5
- 230000005496 eutectics Effects 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 13
- 239000002699 waste material Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910052790 beryllium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000004566 building material Substances 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 239000010881 fly ash Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910001570 bauxite Inorganic materials 0.000 claims description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 3
- 150000001649 bromium compounds Chemical class 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000004567 concrete Substances 0.000 claims description 3
- 239000013256 coordination polymer Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010433 feldspar Substances 0.000 claims description 3
- 150000004673 fluoride salts Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical class BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052627 muscovite Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 150000004760 silicates Chemical class 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 230000008646 thermal stress Effects 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 claims description 3
- 239000012855 volatile organic compound Substances 0.000 claims description 3
- 239000002918 waste heat Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000011964 heteropoly acid Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 239000003440 toxic substance Substances 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical group [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003657 drainage water Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 229910000471 manganese heptoxide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002351 wastewater Substances 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a harmless treatment method of industrial waste salt, which comprises the steps of carrying out high-temperature oxidation and harmless decomposition on organic matters in the industrial waste salt, soluble alkali metal salt, alkaline earth metal salt, heavy metal and a conversion aid component at high temperature, carrying out reactions such as melting, crystal deconstruction, erosion, mineralized matter precursor generation, solid solution reconstruction, low-temperature eutectic matter generation and the like on the industrial waste salt, and quenching and cooling a liquid molten mass generated by the reaction to finally obtain a compact solid solution product; the method has the advantages that toxic organic matters in the industrial waste salt are thoroughly decomposed in a harmless manner at high temperature, precursors synthesized from dioxin POPs toxic substances which cannot be avoided by conventional high-temperature treatment are eliminated from the source, soluble inorganic salt components and heavy metals in the industrial waste salt are sealed in a compact solid solution material network structure, the risk of environmental dissolution is avoided, resource utilization can be realized, and the industrial waste salt can be treated on a large scale, and the method has high automation degree, low treatment cost and the like.
Description
Technical Field
The invention belongs to the technical field of harmless treatment of hazardous solid wastes, and particularly relates to a method for harmless treatment and resource utilization of industrial waste salt.
Background
The industrial waste salt mainly comes from the industries of coal chemical industry, petrochemical industry, medicine, fine chemical industry, printing and dyeing, drilling fluid for petroleum and natural gas exploitation, mine drainage water treatment, solid waste/waste incineration fly ash and the like, and the main salt production link comprises reaction salt generated by mother liquor (process wastewater), neutralization salt generated by acid-base chemical reaction, salt precipitation salt, salt mud generated by distillation residual liquid, salt slag and the like. According to the statistics of an authority, the annual production of industrial waste salt in China at the present stage exceeds 3000 million tons. The industrial waste salt generally has the characteristics of complex components, high potential ecological environment safety risk and the like, and becomes a 'neck' problem restricting the development of enterprises and large-scale chemical industry parks. At present, the high-temperature incineration method is mainly used for treatment in modes of high-temperature incineration, rigid landfill and the like, but the high-temperature incineration method generally has the technical defects of easy melting and volatilization of inorganic salt, synergistic corrosion of high-temperature molten salt, erosion, expansion and stripping of refractory linings of incineration equipment, sintering blockage, high system energy consumption, complex flow, high energy consumption and the like. Rigid landfill has strict requirements on site selection, high-salt solid waste is concentrated and temporarily stored after being pretreated by cement solidification, asphalt solidification and the like, soluble salt in the high-salt solid waste has strong erosion and destruction effects on rigid landfill structures, and potential environmental safety hazards still exist.
Therefore, there is a need to develop a technology that can completely and harmlessly decompose toxic organic matters in industrial waste salt, completely convert heavy metals and soluble components into harmless substances to the environment, and realize resource utilization.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a harmless treatment method for industrial waste salt, which can thoroughly and harmlessly decompose organic matters contained in the industrial waste salt, convert other soluble salts and heavy metal ions which are harmful to the ecological environment in the industrial waste salt into stable melts which are harmless to the environment and recycle the melts.
In order to achieve the purpose, the application adopts the following technical scheme:
a harmless treatment method for industrial waste salt comprises the following steps:
(1) preparing coarse materials by mixing industrial waste salt, auxiliary materials and a conversion auxiliary agent according to the effective chemical reaction amount of a target product, and preparing powder materials with water content less than 10 wt% and particle size less than 2mm by mechanical crushing and screening equipment;
(2) sending the powder material prepared in the step (1) into a waste salt converter, and carrying out high-temperature oxidation and harmless decomposition of organic matters in industrial waste salt, melting, crystal deconstruction, corrosion, mineralized matter precursor generation, solid solution reconstruction and low-temperature eutectic substance generation reaction on the soluble alkali metal salt, the alkaline earth metal salt, the heavy metal and the conversion aid component at the high temperature of 1000-1500 ℃, so that the powder material is converted into a liquid molten mass;
(3) discharging the liquid molten mass generated by converting the industrial waste salt in the step (2) into a quenching chamber through a flow diverter, wherein the high-temperature molten mass is in a range of 10 DEG in the quenching chamber-3～10-2Rapidly cooling to 20-200 ℃ within the time scale, and converting into atypical crystals or amorphous solid solution substances under the condition of thermal stress sudden change;
(4) and (3) enabling the flue gas generated in the waste salt conversion furnace in the step (2) to enter a subsequent waste heat recovery system, generating high-quality steam through a heat exchange system, then entering a subsequent gas purification system, and removing toxic and harmful components in the flue gas to achieve the standard and discharge.
Further, the mass ratio of the transformation aid to the industrial waste salt is 1:5-2: 1; the conversion auxiliary agent is one or more than two of glass powder, red mud, silica sand, feldspar, paratotite, muscovite, kaolin, clay, bauxite and fly ash.
Further, the quenching medium in the step (3) is a compound quenching agent consisting of one or more than two of water, quenching oil and an organic polymer catalyst.
Further, the addition amount of the auxiliary materials is 20-80% of the treatment amount of the industrial waste salt; the auxiliary materials are one or more than two of natural gas, coal gangue, high organic waste, waste tar and combustible VOCs.
Further, the viscosity of the liquid molten mass generated in the step (2) is 20-100 CP.
Further, the heat required by the reaction process in the step (2) is provided by the reaction heat released by the oxidation of the added auxiliary materials and oxygen.
Furthermore, the generated atypical crystal or amorphous solid solution substance is used as a porous adsorption material, concrete fine aggregate, cement admixture and other building materials for resource recycling.
Further, the atypical crystal or amorphous solid substance produced is Na2O-CaO-Al2O3-SiO2Is a glass body, and the chemical composition of the glass phase solid solution is Na2O·Al2O3·6SiO2、Na2O·2Al2O3·6SiO2·2H2O、Na2O·Al2O3·3SiO2·2H2O、3CaO·Al2O3·CaCl2·10H2O、11CaO·7Al2O3·CaCl2、Na12[(AlO2)12(SiO2)12]·27H2O、Ca7(SiO4)2Cl6、(Na4Al3Si3O12Cl)3CaO·Fe2O3·CaCl2·10H2Two or more of O.
Further, the soluble alkali metal and alkaline earth metal salts in the industrial waste salt include two or more of chlorides, fluorides, bromides, hypochlorites, chlorates, hypobromites, bromates, sulfides, sulfates, thiosulfates, sulfites, nitrates, carbonates, phosphates/polyphosphates, silicates and aluminates of Li, Na, K, Ca, Be, Mg, Sr and Ba.
Furthermore, soluble alkali metal and alkaline earth metal salts in the industrial waste salt also comprise NH4One or more of sulfonate, organic carboxylate and heteropoly acid salt of Li, Na, K, Ca, Be, Mg, Sr and Ba; the heavy metals in the industrial waste salt comprise As, Cu, Zn, Se, Cd, Hg, Pb, Cr and Ni and waterA compound existing in a soluble state, an exchangeable state, an acid soluble state, an organic combination state, an oxidation state and a ferro-manganese oxidation state.
The invention can realize the following beneficial effects:
1. the harmless treatment method of the industrial waste salt provided by the invention can thoroughly and harmlessly decompose toxic organic matters in the industrial waste salt at high temperature, and eliminates precursors synthesized by dioxin POPs toxic substances which cannot be avoided by conventional high-temperature treatment from the source.
2. According to the harmless treatment method for the industrial waste salt, under the synergistic effect of high temperature and the conversion aid, the soluble inorganic salt component and heavy metal in the industrial waste salt are sealed in a compact solid solution material network structure, so that the risk of environmental dissolution is avoided, and the resource utilization can be realized.
3. The method for harmless treatment of industrial waste salt provided by the invention has no special limitation on the composition of the industrial waste salt, can realize the harmless treatment of the industrial waste salt, particularly the organic industrial waste salt in a wider range, and can recycle the converted product as cement auxiliary materials, building materials and the like.
4. The harmless treatment method for industrial waste salt provided by the invention can realize large-scale treatment of the industrial waste salt, and has the advantages of thorough decomposition of harmful substances, high environmental safety, continuous and integrated production, convenience in operation, high automation degree, low treatment cost and the like.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below.
The invention relates to a harmless treatment method of industrial waste salt, which comprises the steps of respectively drying, dehydrating, forming, granulating and screening the industrial waste salt, the transformation auxiliary agent and auxiliary materials, then carrying out high-temperature oxidation and harmless decomposition on organic matters in the industrial waste salt under a high-temperature condition, carrying out reactions such as melting, crystal deconstruction, fusion corrosion, mineralized matter precursor generation, solid solution reconstruction, low-temperature eutectic substance generation and the like on the components of soluble alkali metal salt, alkaline earth metal salt, heavy metal and the transformation auxiliary agent, discharging liquid molten mass generated by the reactions from a drainage device at the lower part of a waste salt converter, entering a quenching chamber, and finally obtaining a compact solid solution product after quenching and cooling.
The soluble alkali metal and alkaline earth metal salts in the industrial waste salt comprise two or more of inorganic salts and oxides of Li, Na, K, Ca, Be, Mg, Sr and Ba, such as chlorides, fluorides, bromides, hypochlorites, chlorates, hypobromites, bromates, sulfides, sulfates, thiosulfates, sulfites, nitrates, carbonates, phosphates/polyphosphates, silicates, aluminates and the like.
Soluble alkali metal and alkaline earth metal salts in the industrial waste salt also comprise NH4And one or more organic salts such as sulfonates, organic carboxylates, and heteropolyacids of Li, Na, K, Ca, Be, Mg, Sr, and Ba.
The heavy metal in the industrial waste salt comprises a compound which exists in the occurrence forms of water-soluble state, exchangeable state, acid-soluble state, organic combination state, oxidation state, iron-manganese oxidation state and the like of heavy metal elements such As As, Cu, Zn, Se, Cd, Hg, Pb, Cr, Ni and the like.
The transformation auxiliary agent is two or more than two minerals rich in silicon and aluminum substances, such as glass powder, red mud, silica sand, feldspar, paraphrase, muscovite, kaolin, clay, bauxite, fly ash and the like.
The conversion aid and the industrial waste salt are matched in proportion according to a free oxygen determination coefficient R ═ A/B ═ 0.1-2.0 (A ═ Al)2O3、SiO2、B2O3、As2O3、SO3、P2O5、CrO3、Mn2O7、Fe2O3、TiO2、WO3And Sb2O3；B＝Li2O、Na2O、K2O、Ni2O、CaO、BeO、MgO、SrO、BaO、CuO、ZnO、Se、CdO、HgO、PbO、PbO2)
The invention relates to a harmless treatment method of industrial waste salt, which comprises the following specific steps:
(1) industrial waste salt, auxiliary materials and conversion auxiliary agents are mixed according to the effective chemical reaction amount of a target product to prepare coarse materials, and the coarse materials are prepared into powder materials with water content less than 10 wt% and particle size less than 2mm through mechanical crushing and screening equipment;
(2) conveying the qualified powder material prepared in the step (1) through a mechanical-pneumatic coupling type powder feeding system, performing high-temperature conversion, and performing chemical chain conversion reaction at the high temperature of 1000-1500 ℃ to convert the qualified powder material into a liquid melt;
(3) discharging the liquid molten mass generated by converting the industrial waste salt in the step (2) into a quenching chamber through a flow diverter, wherein the high-temperature molten mass is 10 DEG in the quenching chamber-3～10-2Rapidly cooling to 20-200 ℃ within the time scale, and converting into atypical crystals or amorphous solid solution substances under the condition of thermal stress sudden change;
(4) and (3) enabling the flue gas generated in the waste salt conversion furnace in the step (2) to enter a subsequent waste heat recovery system, generating high-quality steam through a high-efficiency heat exchange system, then entering a subsequent gas purification system, and removing toxic and harmful components in the flue gas to achieve the standard and discharging.
The mass ratio range of the transformation auxiliary agent to the industrial waste salt is as follows: 1:5-2:1.
The heat source required by the reactions of chemical oxidative decomposition of organic matters contained in industrial waste salt in the waste salt conversion furnace, melting of soluble salt and conversion aid components, crystal deconstruction, erosion, mineralized matter precursor generation, solid solution reconstruction and the like can be provided by reaction heat released by oxidation of added auxiliary materials and oxygen.
The quenching medium is a compound quenching agent consisting of one or more than two of water, quenching oil and an organic polymer catalyst.
The viscosity range of the liquid molten mass generated in the step (2) is 20-100 CP. The auxiliary materials for providing a heat source for complete decomposition of organic matters in the industrial waste salt and conversion reaction of the waste salt can be one or more than two of combustible materials such as natural gas, coal gangue, high organic matter waste, waste tar, combustible VOCs and the like.
The addition amount of the auxiliary materials is 20-80% of the treatment amount of the industrial waste salt.
The atypical crystal or amorphous solid solution substance generated after the conversion of the industrial waste salt can be used as a porous adsorption material, concrete fine aggregate, cement admixture and other building materials for resource recycling.
The atypical crystal or amorphous solid solution substance generated after the industrial waste salt is converted is mainly Na2O-CaO-Al2O3-SiO2Is a glass body, and the main chemical composition of the glass phase solid solution is Na2O·Al2O3·6SiO2、Na2O·2Al2O3·6SiO2·2H2O、Na2O·Al2O3·3SiO2·2H2O、3CaO·Al2O3·CaCl2·10H2O、11CaO·7Al2O3·CaCl2、Na12[(AlO2)12(SiO2)12]·27H2O、Ca7(SiO4)2Cl6、(Na4Al3Si3O12Cl)3CaO·Fe2O3·CaCl2·10H2Two or more of O.
Claims (10)
1. A harmless treatment method for industrial waste salt is characterized by comprising the following steps:
(1) preparing coarse materials by mixing industrial waste salt, auxiliary materials and a conversion auxiliary agent according to the effective chemical reaction amount of a target product, and preparing powder materials with water content less than 10 wt% and particle size less than 2mm by mechanical crushing and screening equipment;
(2) feeding the powder material prepared in the step (1) into a waste salt converter, and carrying out high-temperature oxidation and harmless decomposition of organic matters in industrial waste salt, melting, crystal deconstruction, erosion, mineralized matter precursor generation, solid solution reconstruction and low-temperature eutectic matter generation reaction of soluble alkali metal salt, alkaline earth metal salt, heavy metal and conversion aid components at the high temperature of 1000-1500 ℃, so that the powder material is converted into a liquid molten matter;
(3) discharging the liquid molten mass generated by converting the industrial waste salt in the step (2) into a quenching chamber through a flow diverter, wherein the high-temperature molten mass is in a range of 10 DEG in the quenching chamber-3～10-2Time scale ofRapidly cooling to 20-200 ℃ in the interior, and converting into atypical crystals or amorphous solid solution substances under the condition of sudden change of thermal stress;
(4) and (3) enabling the flue gas generated in the waste salt conversion furnace in the step (2) to enter a subsequent waste heat recovery system, generating high-quality steam through a heat exchange system, then entering a subsequent gas purification system, and removing toxic and harmful components in the flue gas to achieve the standard and discharge.
2. The method for harmless treatment of industrial waste salt according to claim 1, characterized in that: the mass ratio of the conversion auxiliary agent to the industrial waste salt is 1:5-2: 1; the conversion auxiliary agent is one or more than two of glass powder, red mud, silica sand, feldspar, paraphrate, muscovite, kaolin, clay, bauxite and fly ash.
3. The method for harmless treatment of industrial waste salt according to claim 1, characterized in that: the quenching medium in the step (3) is a compound quenching agent consisting of one or more than two of water, quenching oil and an organic polymer catalyst.
4. The method for harmless treatment of industrial waste salt according to claim 1, characterized in that: the addition amount of the auxiliary materials is 20-80% of the treatment amount of the industrial waste salt; the auxiliary materials are one or more than two of natural gas, coal gangue, high organic waste, waste tar and combustible VOCs.
5. The method for harmless treatment of industrial waste salt according to claim 1, characterized in that: the viscosity of the liquid molten mass generated in the step (2) is 20-100 CP.
6. The method for harmless treatment of industrial waste salt according to claim 1, characterized in that: the heat required in the reaction process of the step (2) is provided by the reaction heat released by the oxidation of the added auxiliary materials and oxygen.
7. The method for harmless treatment of industrial waste salt according to claim 1, characterized in that: the generated atypical crystal or amorphous solid solution substance is used as a porous adsorption material, concrete fine aggregate, cement admixture and other building materials for resource recycling.
8. The method for harmless treatment of industrial waste salt according to claim 1, characterized in that: the atypical crystal or amorphous solid solution substance is Na2O-CaO-Al2O3-SiO2Is a glass body, and the chemical composition of the glass phase solid solution is Na2O·Al2O3·6SiO2、Na2O·2Al2O3·6SiO2·2H2O、Na2O·Al2O3·3SiO2·2H2O、3CaO·Al2O3·CaCl2·10H2O、11CaO·7Al2O3·CaCl2、Na12[(AlO2)12(SiO2)12]·27H2O、Ca7(SiO4)2Cl6、(Na4Al3Si3O12Cl)3CaO·Fe2O3·CaCl2·10H2Two or more of O.
9. The method for harmless treatment of industrial waste salt according to claim 1, characterized in that: the soluble alkali metal and alkaline earth metal salts in the industrial waste salt comprise two or more of chlorides, fluorides, bromides, hypochlorites, chlorates, hypobromites, bromates, sulfides, sulfates, thiosulfates, sulfites, nitrates, carbonates, phosphates/polyphosphates, silicates and aluminates of Li, Na, K, Ca, Be, Mg, Sr and Ba.
10. The method for harmless treatment of industrial waste salt according to claim 1, characterized in that: soluble alkali metal and alkaline earth metal salts in the industrial waste salt also comprise NH4、Li、Na、K、Ca. One or more of sulfonate, organic carboxylate and heteropoly acid salt of Be, Mg, Sr, Ba, etc.; the heavy metal in the industrial waste salt comprises compounds in the forms of As, Cu, Zn, Se, Cd, Hg, Pb, Cr and Ni in water soluble state, exchangeable state, acid soluble state, organic combination state, oxidation state and ferro-manganese oxidation state.
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| CN117105549A (en) * | 2023-10-25 | 2023-11-24 | 常熟理工学院 | Method for preparing magnesium cement cementing material by using industrial waste salt and product thereof |
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