CN113798311A - Method for removing cyanide in metal heat treatment residues by synergistic action of sensitizer and microwave - Google Patents
Method for removing cyanide in metal heat treatment residues by synergistic action of sensitizer and microwave Download PDFInfo
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000010438 heat treatment Methods 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 230000002195 synergetic effect Effects 0.000 title description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 10
- 239000011707 mineral Substances 0.000 claims abstract description 10
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052595 hematite Inorganic materials 0.000 claims description 11
- 239000011019 hematite Substances 0.000 claims description 11
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 230000001235 sensitizing effect Effects 0.000 claims 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 12
- 239000007790 solid phase Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 150000002825 nitriles Chemical class 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- -1 etc. Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000007255 decyanation reaction Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- MWEXRLZUDANQDZ-RPENNLSWSA-N (2s)-3-hydroxy-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-(3-methylsulfanylpropyl)triazol-1-y Chemical compound N1=NC(CCCSC)=CN1[C@@H](CO)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 MWEXRLZUDANQDZ-RPENNLSWSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UJGOCJFDDHOGRX-UHFFFAOYSA-M [Fe]O Chemical compound [Fe]O UJGOCJFDDHOGRX-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000001107 thermogravimetry coupled to mass spectrometry Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The invention provides a method for removing cyanide in metal heat treatment residues by the cooperation of a sensitizer and microwaves, which comprises the following steps: adding mineral particles rich in iron oxide as a sensitizer into the solid metal heat treatment residues, and fully stirring and uniformly mixing to obtain a solid initial material; and (3) subjecting the obtained solid initial material to microwave treatment in an aerobic state, wherein the microwave treatment power is 600-900W, the microwave treatment time is 120-240 s, the solid initial material is firstly converted into cyanate and ferricyanate under the microwave treatment, and the cyanate and ferricyanate are further oxidized to generate carbonate, nitrogen, carbon dioxide and iron oxide. The method not only can realize the harmless removal of the cyanogen-containing residues in a solid phase system, but also has the advantages of wide raw material source, high cyanogen removal efficiency, simple process, low treatment cost, safety, environmental protection and the like.
Description
Technical Field
The invention relates to the technical field of harmless treatment of solid hazardous waste, in particular to a method for removing cyanide in metal heat treatment residues.
Background
The metal heat treatment cyanide-containing residues come from the industries of metal surface treatment, heat treatment processing and the like, and mainly comprise quenching bath residues generated by metal heat treatment by using cyanides, quenching wastewater treatment sludge, waste linings generated in the maintenance process of a cyanide-containing heat treatment furnace, carburizing cyanide residues, cyanide-containing residues generated by cleaning a salt bath kettle of a metal heat treatment process and the like. At present, the method for removing cyanide from cyanide-containing residues in metal heat treatment mainly comprises the following steps: chlorine oxidation, inconel process, hydrogen peroxide oxidation, ozone oxidation, incineration, natural degradation, and the like.
The chlorine oxidation method is to decompose cyanide in the cyanide slag into low-toxicity or non-toxicity substances by adopting a chlorine oxidant under an alkaline condition. Common oxychlorinating agents include chlorine dioxide, sodium hypochlorite, calcium hypochlorite, liquid chlorine, chlorine gas, and the like. The method is mature, is widely applied at home and abroad, has simple equipment and can be operated intermittently or continuously, but the method can not recover cyanide, is easy to generate CNCl to cause secondary pollution, and chloride ions accumulated in water can corrode the equipment and the pipeline, and surface water and soil salinization are easy to cause in the process of piling up the treated cyanide residues.
The method is also called sulfur dioxide-air method, and uses sulfur dioxide or a medicament capable of generating sulfur dioxide and air as an oxidant to remove cyanide in residues under the catalysis of copper ions. The commonly used agents include sodium sulfite, sodium pyrosulfite, etc., and a gas containing sulfur dioxide may be used instead of the solid agent. The method has the advantages of simple process, wide medicament source, low equipment investment and remarkable cyanide removal effect. However, because of the weak oxidizing power of sulfur dioxide, the ore pulp must be kept at a higher concentration to achieve a better decyanation effect.
The hydrogen peroxide oxidation method takes hydrogen peroxide as an oxidant and oxidizes cyanide into a non-toxic compound under the catalysis of copper ions and under the alkaline condition. The hydrogen peroxide belongs to a cleaning agent, a reaction product is water, secondary pollution is avoided, but the direct oxidation effect on the ferricyanide complex is not good, and the method is suitable for decyanation treatment of cyanide slag with low content of the ferricyanide complex or containing metal ions capable of forming precipitates with the ferricyanide complex. In addition, hydrogen peroxide belongs to a strong oxidant, has strong corrosivity and high risk of storage and transportation, and is listed as a major risk source.
The ozone oxidation method adopts ozone as an oxidant to oxidize and remove cyanide in the cyanide residue. Ozone has a strong oxidizing power and can oxidize cyanides into carbonates and nitrogen. The method has simple process, does not need to add other reagents, does not generate secondary pollutants in the oxidation process, is a clean oxidation method, and is suitable for treating the cyanide slag containing medium and low concentration cyanides. However, ozone needs to be provided by an ozone generator, so that the equipment investment is relatively high, the maintenance is difficult, and the energy consumption is high.
The burning method is that the cyanogen slag is put into a burning furnace, and toxic substances containing cyanogen are decomposed into CO under a certain high temperature condition2、N2、H2O, ash and a small amount of harmless compounds, the incineration temperature is generally controlled to be more than 800 ℃, the cyanide removal rate reaches more than 99 percent, and the treated solid phase can completely meet the discharge requirement of the cyanide slag. However, the method has extremely high energy consumption, and the cyanogen slag and other ores or tailings are usually burnt together to extract valuable substances or are comprehensively utilized after being burnt.
The intensified natural degradation method utilizes the characteristic that cyanide is easy to decompose and decomposes under the action of a plurality of factors such as illumination, temperature, moisture, oxygen content and the like. After the cyanide tailings reach a specific water content through solid-liquid separation, the cyanide tailings are subjected to enhanced degradation under natural conditions through operations such as turning, airing, rolling and the like, so that the cyanide content in the cyanide tailings is reduced. The method is suitable for arid areas such as northwest where the evaporation intensity is far greater than the rainfall intensity, and the treatment of cyanide residues containing low concentration cyanide.
The biodegradation process is to hydrolyze cyanide into formamide or into carbon dioxide and ammonia by using some microbes which have special enzyme systems and metabolize cyanide as carbon and nitrogen sources. Cyanide and thiocyanide are generally degraded by using pseudo-unicellular Paacllmobilis bacteria, and the equipment is a rotating biological contactor. The method has the problems of poor adaptability, low treatment speed, low treatment concentration, large occupied area and the like.
Chinese patent document CN108579659A discloses a method for treating cyanide-containing waste liquid by adsorbing cyanide in a cyanide-containing solution with a ferromagnetic adsorbent, which can not only generate strong acid-soluble cyanide through a complex reaction with free cyanide and thiocyanate in the cyanide-containing solution, but also adsorb the generated strong acid-soluble cyanide with active hydroxyl iron on the surface of the ferromagnetic adsorbent, thereby removing the cyanide in the solution and realizing recovery. However, the method is only suitable for liquid-phase reaction systems, and cyanide is collected in the reaction process and is not completely converted into harmless substances through chemical reaction.
Chinese patent document CN111675395A discloses a method for degrading Cu-containing metal by microwave assistance2+And metallic Fe2+The method for preparing cyanide ion from ion ore dressing waste water includes the first letting Fe2+Ion and cyanide ion generate ferrous blue and ferric blue precipitate under acidic condition, filtering, and heating the mother liquid with Cu under microwave2+Catalyzing hydrogen peroxide to oxidize cyanogen ions in the mother liquor, and hydrolyzing cyanate obtained by oxidation into ammonium ions and carbonate ions or bicarbonate ions. The method is only suitable for liquid phase reaction systems, and the use of hydrogen peroxide has larger risk.
In summary, although there are many methods for treating cyanide-containing waste residues in the prior art, most methods are only suitable for liquid phase reaction systems, and there is still a need to develop a more suitable, safer and environmentally friendly method for removing cyanide solid phase from cyanide-containing waste residues generated by heat treatment of metals.
Disclosure of Invention
In view of the above technical background, the present invention aims to: the method for removing the cyanide in the metal heat treatment residues by the aid of the sensitizer and microwaves can achieve harmless removal of cyanide-containing residues in a solid phase system, and has the advantages of wide raw material source, high cyanide removal efficiency, simple process, low treatment cost, safety, environmental friendliness and the like.
The above object of the present invention is achieved by the following technical solutions:
a method for removing cyanide in metal heat treatment residues by the synergy of a sensitizer and microwaves is provided, and the method comprises the following steps:
1) adding mineral particles rich in iron oxide as a sensitizer into the solid metal heat treatment residues, and fully stirring and uniformly mixing to obtain a solid initial material;
2) treating the solid initial material obtained in the step 1) by using microwaves in an aerobic state, firstly converting the solid initial material into cyanate and ferricyanate under the microwave treatment, and further oxidizing the cyanate and the ferricyanate to generate carbonate, nitrogen, carbon dioxide and iron oxide.
The process of the invention is directed to heat-treated metal residues, such solid residues usually containing cyanide based on sodium cyanide, the cyanide content of conventional heat-treated metal residues being determined as CN-It is about 500 mg/kg. The method is verified by means of XRD, TG-MS, gas component detection and the like, and the reaction process of the solid initial material under microwave treatment in the step 2) of the method is shown in the following formulas (1) - (3):
according to the reaction process, the iron oxide-rich mineral particles are used as a sensitizer in a solid phase reaction system to play a good role in catalysis, the iron oxide component has strong wave absorbing property, and is excited to have extremely high catalytic activity after absorbing the radiation energy of a light wave in a microwave electromagnetic field, and the high-activity iron oxide component is subjected to catalytic reaction with cyanide in residues in the microwave field, so that the cyanide in the metal heat treatment residues can be quickly and thoroughly converted into non-toxic and harmless substances, and the aim of harmless treatment is really achieved.
In the method of the present invention, the iron oxide-rich mineral particles of 1) may be derived from a plurality of different existing natural ores. In a preferred embodiment of the present invention, the natural ore is natural iron ore, and further preferably natural iron ore with an iron oxide content of not less than 50%; the natural iron ore with the content of the iron oxide components not less than 50 percent can be selected from any one or a composition of more than two of magnetite, hematite, maghemite or limonite; more preferably magnetite or hematite; most preferably hematite.
In the scheme of the invention, the size of the mineral particles rich in iron oxide in 1) can influence the wave-absorbing catalytic performance of the mineral particles, so that the removal effect of cyanide in residues is influenced, the transmission performance of microwave is reduced due to the increase of particle compactness when the particle size is too large, the wave-absorbing performance is influenced due to the reduction of material dielectric constant when the particle size is too small, and the catalytic performance of a sensitizer is reduced. Therefore, in a preferred embodiment of the present invention, the particle size of the iron oxide-rich mineral particles in 1) is 100-400 mesh, and the optimal particle size is 200-300 mesh.
In the scheme of the invention, in the solid starting material 1), the reaction of the material can be effectively catalyzed only by using a proper amount of the sensitizer, so that the proportion of the sensitizer in the solid starting material 1) to the treated residue needs to be controlled. In a preferred embodiment of the present invention, 1) specifically, natural iron ore having an iron oxide content of not less than 50% is added as a sensitizer to the metal heat-treatment residue having a cyanide content of 500mg/kg, and the weight ratio of the sensitizer to the metal heat-treatment residue is controlled to be 0.1 to 1, more preferably 0.2 to 0.6, and most preferably 0.3 to 0.4.
In the preferable scheme of the invention, the full stirring and the uniform mixing in the step 1) are uniformly mixed by adopting a dry stirrer, the rotating speed of the stirrer is more than 200 r/min, and the mixing time is more than 10 min.
In the scheme of the invention, the microwave treatment in the step 2) can obviously accelerate the catalysis of the iron oxide to the reaction, but experiments show that the power and the time of the microwave treatment have a certain relation with the reaction effect. If the microwave power is too small or the time is too short, the sensitizer cannot obtain enough excitation energy, so that the catalytic performance of the sensitizer is reduced; if the microwave power is too high or the microwave power is too long, on one hand, the sintering phenomenon among materials can occur, the compact sintering layer is coated on the particle surface, the reaction can be blocked or delayed, and on the other hand, the great energy waste can be caused. Therefore, in a preferred scheme of the invention, the microwave treatment power of 2) is 600-900W, and the microwave treatment time is 120-240 s; further preferably, the microwave power is 700-800W, and the microwave treatment time is 120-180 s; most preferably 700W processing 180s or 800W processing 120 s.
The method for removing cyanide in metal heat treatment residues by the aid of the sensitizer and microwaves in a synergistic manner has the following basic principles: cyanide in the metal heat treatment residue has weak wave absorbing capability in a microwave field, and is difficult to effectively remove by single microwave irradiation. The introduction of the sensitizer can obviously increase the absorption of microwave energy and convert the microwave energy into heat energy, so that the point position of the surface of the sensitizer is quickly heated to high temperature to form a high-activity site, and cyanide in the metal heat treatment residue is contacted with iron oxide in the sensitizer at the high-activity site to quickly generate catalytic reaction to generate sodium carbonate, nitrogen, carbon dioxide and the like. In addition, the microwave energy can make polar molecules rotate and vibrate rapidly, so that the polar molecules are in a higher excited state, the collision chance of reactant molecules is increased, the activation energy of chemical reaction is reduced, the thermodynamics of cyanide reaction is changed, the cyanide reaction is accelerated under the catalytic action, and therefore the cyanide in the residues is effectively removed, and the purpose of harmless treatment of the residues is finally achieved. Under the inventive concept of the invention, the number and spatial distribution of high active sites in the material can be regulated and controlled by changing the type, fineness, addition amount and other conditions of the sensitizer within a certain range, and the effective removal of cyanide in the metal heat treatment residues is finally realized by assisting in the regulation of microwave power and microwave time. The method not only can realize the harmless removal of the cyanogen-containing residues in a solid phase system, but also has the advantages of wide raw material source, high cyanogen removal efficiency, simple process, low treatment cost, safety, environmental protection and the like. After the metal heat treatment residues are treated by the method, the total cyanogen content can be reduced to be below 5mg/L, and the national hazardous solid waste discharge standard is reached. The method can be widely applied to the fields of metal processing, building materials, metallurgy, chemical engineering and the like.
Detailed Description
The invention provides a method for removing cyanide in metal heat treatment residues by the cooperation of a sensitizer and microwaves, which specifically comprises the following steps:
(1) and (4) preparing raw materials. Drying, crushing and screening the metal heat treatment residues for later use.
(2) A sensitizer is prepared. Selecting natural iron ore rich in iron oxide as a sensitizer, removing impurities, crushing and screening for later use.
(3) And (4) mixing the materials. Weighing the metal heat treatment residues in the step (1) and the sensitizer in the step (2) according to a certain proportion, adopting a dry-type stirrer mixing mode, reasonably adjusting the rotating speed of the stirrer, and mixing the materials uniformly after a certain stirring time.
(4) And removing cyanide. And (4) adding the mixed material in the step (3) into a microwave device, reasonably adjusting the microwave power, and removing cyanide in the metal heat treatment residues after a certain microwave irradiation time.
The above-described scheme and effects thereof will be specifically described below by way of examples and comparative examples, which are not intended to limit the scope of the present invention.
In each of the examples and comparative examples, a metal heat treatment residue having a cyanide content of about 500mg/kg was treated, and the iron oxide content in the sensitizer was not less than 50%.
Example 1
10g of the metal heat treatment residue and 2g of magnetite with the particle size of 100-200 meshes are mixed, the rotation speed of a stirrer is 200 r/min, and the mixing time is 10 min. Then, the mixed material is added into a microwave oven, the microwave power is 600W, the microwave time is 240s, and after treatment, the cyanide content in the residue is 4.5mg/kg, which is reduced by more than 99 percent compared with the original cyanide content.
Example 2
10g of the metal heat treatment residues are mixed with 10g of hematite with the particle size of 300-400 meshes, the rotating speed of a stirrer is 200 r/min, and the mixing time is 20 min. Then, the mixed material is added into a microwave oven, the microwave power is 700W, the microwave time is 180s, and after treatment, the cyanide content in the residue is 2.3mg/kg, which is reduced by more than 99.5 percent compared with the original cyanide content.
Example 3
10g of the metal heat treatment residue and 10g of magnetite with the particle size of 300-400 meshes are mixed, the rotating speed of a stirrer is 200 r/min, and the mixing time is 20 min. Then, the mixed material is added into a microwave oven, the microwave power is 700W, the microwave time is 180s, and after treatment, the cyanide content in the residue is 3.8mg/kg, which is reduced by more than 99 percent compared with the original cyanide content.
Example 4
10g of the metal heat treatment residues are mixed with 10g of limonite with the grain diameter of 300-400 meshes, the rotating speed of a stirrer is 200 r/min, and the mixing time is 20 min. Then, the mixed material is added into a microwave oven, the microwave power is 700W, the microwave time is 180s, and after treatment, the cyanide content in the residue is 4.1mg/kg, which is reduced by more than 99 percent compared with the original cyanide content.
Example 5
10g of the metal heat treatment residues are mixed with 4g of hematite with the particle size of 200-300 meshes, the rotating speed of a stirrer is 200 r/min, and the mixing time is 20 min. Then, the mixed material is added into a microwave oven, the microwave power is 800W, the microwave time is 120s, and after treatment, the cyanide content in the residue is 1.2mg/kg, which is reduced by more than 99.5 percent compared with the original cyanide content.
Example 6
10g of the metal heat treatment residues are mixed with 1g of hematite with the particle size of 200-300 meshes, the rotating speed of a stirrer is 200 r/min, and the mixing time is 20 min. Then, the mixed material is added into a microwave oven, the microwave power is 800W, the microwave time is 120s, and after treatment, the cyanide content in the residue is 3.7mg/kg, which is reduced by more than 99 percent compared with the original cyanide content.
Example 7
10g of the metal heat treatment residues are mixed with 4g of hematite with the particle size of 100-200 meshes, the rotating speed of a stirrer is 200 r/min, and the mixing time is 20 min. Then, the mixed material is added into a microwave oven, the microwave power is 800W, the microwave time is 120s, and after treatment, the cyanide content in the residue is respectively 2.1mg/kg, which is reduced by more than 99.5 percent compared with the original cyanide content.
Comparative example 1
Compared with the treatment of the example 1, 10g of the metal heat treatment residue is directly added into a muffle furnace without adding any sensitizer, the heating temperature is 700 ℃, the heating time is 240s, and after the treatment, the cyanide content in the residue is 45.2mg/kg, which is 10-38 times of the cyanide content after the treatment of the examples 1-3.
Comparative example 2
The sensitizer is added according to the mode of example 1, but microwave treatment is not used, but heating treatment in a muffle furnace is changed, and the method specifically comprises the following steps: 10g of the metal heat treatment residue and 2g of magnetite with the particle size of 100-200 meshes are mixed, the rotation speed of a stirrer is 200 r/min, and the mixing time is 10 min. The mixture was then charged to a muffle furnace at 700 ℃ for 240s, and the cyanide content of the residue after treatment was 21.3mg/kg, which was about 5 times the cyanide content of the residue after treatment in example 1.
Comparative example 3
The microwave treatment is carried out in the manner of reference example 1, but a sensitizer is not added before the microwave treatment, and the method specifically comprises the following steps: 10g of the metal heat treatment residue is directly added into a microwave oven without adding any sensitizer, the microwave power is 600W, the microwave time is 240s, and after treatment, the cyanide content in the residue is 41.8mg/kg, which is 9 times of the cyanide content after the treatment of the example 1.
Comparative example 4
The metal heat treatment residue was treated in the same manner as in example 5 except that the microwave treatment time was changed to 60 seconds, and the cyanide content in the residue after the treatment was 21.2mg/kg, which was about 18 times the cyanide content after the treatment in example 5.
Comparative example 5
The residue of the above metal heat treatment was treated in the same manner as in example 5 except that the microwave treatment power was changed to 600W and the conditions were not changed, whereby the cyanide content in the residue was 19.8mg/kg, which was about 17 times the cyanide content after the treatment in example 5.
Comparative examples 6 to 7
The above metal heat treatment residue was treated in the same manner as in example 5 except that the sensitizer was changed to ilmenite and siderite, respectively, and the conditions were not changed, and the cyanide content in the residue after the treatment was 18.2mg/kg and 14.8mg/kg, respectively, which were about 15 times and 12 times as high as those of the residue after the treatment of example 5.
Comparative examples 8 to 9
The above-mentioned residue of heat treatment of metals was treated in the same manner as in example 5 except that the microwave treatment time was changed to 15s and 360s, respectively, and the cyanide contents of the residue after the treatment were 128.6mg/kg and 48.4mg/kg, respectively, which were about 107 times and 40 times as high as those of the residue after the treatment in example 5, respectively, without changing the conditions.
Comparative examples 10 to 11
The above-mentioned residue of heat treatment of metals was treated in the same manner as in example 5 except that the microwave treatment power was changed to 400W and 1200W, respectively, and the cyanide contents of the residue after the treatment were 36.2mg/kg and 28.3mg/kg, respectively, which were about 30 times and 24 times as high as those of the residue after the treatment in example 5, respectively, without changing the other conditions.
Comparative examples 12 to 13
The above-mentioned residue of the metal heat treatment was treated in the same manner as in example 5 except that the hematite particle size was changed to 50 mesh and 800 mesh, respectively, and the conditions were not changed, and the cyanide content in the residue after the treatment was 72.5mg/kg and 34.6mg/kg, respectively, which were about 60 times and 29 times as high as those of example 5, respectively.
Claims (7)
1. A method for removing cyanide in metal heat treatment residue by combining a sensitizer and microwave, wherein the content of cyanide in the metal heat treatment residue is 400-600 mg/kg; the method comprises the following steps:
1) adding mineral particles with the iron oxide content of not less than 50% into the solid metal heat treatment residues as a sensitizing agent, controlling the weight ratio of the sensitizing agent to the residues to be 0.1-1, and fully stirring and uniformly mixing to obtain a solid initial material;
2) and (2) treating the solid initial material obtained in the step 1) by using microwaves in an aerobic state, wherein the microwave treatment power is 600-900W, the microwave treatment time is 120-240 s, the solid initial material is firstly converted into cyanate and ferricyanate under the microwave treatment, and the cyanate and ferricyanate are further oxidized to generate carbonate, nitrogen, carbon dioxide and iron oxide.
2. The method of claim 1, wherein: 1) the mineral particles with the iron oxide content of not less than 50 percent are natural iron ore particles selected from any one or a composition of more than two of the following: magnetite, hematite, maghemite or limonite; preferably magnetite or hematite; most preferably hematite.
3. The method of claim 1, wherein: 1) the particle size of the mineral particles rich in the ferric oxide is 100-400 meshes, and the optimal particle size is 200-300 meshes.
4. The method of claim 1, wherein: 1) the weight ratio of the sensitizer to the residue is preferably 0.2 to 0.6, most preferably 0.3 to 0.4.
5. The method of claim 1, wherein: 1) the fully stirring and uniformly mixing adopts a dry-type stirrer for uniformly mixing, the rotating speed of the stirrer is more than 200 r/min, and the mixing time is more than 10 min.
6. The method of claim 1, wherein: 2) the microwave power is 700-800W, and the microwave treatment time is 120-180 s.
7. The method of claim 1, wherein: 2) the microwave treatment is 700W treatment for 180s or 800W treatment for 120 s.
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