WO2001039902A1 - Procede et dispositif de traitement et de conditionnement d'un effluent en vue d'une vitrification - Google Patents
Procede et dispositif de traitement et de conditionnement d'un effluent en vue d'une vitrification Download PDFInfo
- Publication number
- WO2001039902A1 WO2001039902A1 PCT/FR2000/003319 FR0003319W WO0139902A1 WO 2001039902 A1 WO2001039902 A1 WO 2001039902A1 FR 0003319 W FR0003319 W FR 0003319W WO 0139902 A1 WO0139902 A1 WO 0139902A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- effluent
- heating
- chamber
- vitrification
- metal salts
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000004017 vitrification Methods 0.000 title claims abstract description 37
- 230000003750 conditioning effect Effects 0.000 title description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 74
- 150000003839 salts Chemical class 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 28
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 150000001450 anions Chemical class 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims description 28
- 239000000654 additive Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 17
- 238000011282 treatment Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000010791 domestic waste Substances 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002699 waste material Substances 0.000 abstract description 8
- 239000002689 soil Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 37
- 239000007787 solid Substances 0.000 description 17
- 239000003517 fume Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- -1 S0 and C0 2 Chemical class 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010882 bottom ash Substances 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010805 inorganic waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
- B09B3/29—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix involving a melting or softening step
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/005—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture of glass-forming waste materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2202/00—Combustion
- F23G2202/10—Combustion in two or more stages
- F23G2202/104—Combustion in two or more stages with ash melting stage
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2204/00—Supplementary heating arrangements
- F23G2204/20—Supplementary heating arrangements using electric energy
- F23G2204/204—Induction
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/30—Solid combustion residues, e.g. bottom or flyash
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2215/00—Preventing emissions
- F23J2215/60—Heavy metals; Compounds thereof
Definitions
- the present invention relates to a method and a device for treating and conditioning an effluent comprising heavy metal salts with a view to its vitrification.
- effluents are produced for which there is no satisfactory disposal system from the point of view of environmental protection.
- the effluents in question are mainly inorganic waste containing various toxic pollutants, such as heavy metals and their salts, and very particularly, those having a soluble fraction large enough to prohibit their storage in landfill.
- These effluents can be liquid or solid. They can come from any effluent-generating process comprising salts of heavy metals.
- Liquid effluents can come from, for example, chemical surface treatment processes. These effluents are generally acidic and highly charged with metals. Although widespread throughout the national territory, they represent a very large volume of pollution.
- the purification technique generally includes a conventional treatment of neutralization / precipitation which leads to the formation of sludge for storage in a Class I landfill.
- a medium-sized company practicing these processes can generate up to 1 tonne of sludge concentrated in metals per year.
- Solid effluents can come from, for example, household waste incineration processes. These processes actually generate two categories of effluents: solid effluents and gaseous effluents or incineration fumes.
- Solid effluents constitute the mineral fraction of the waste, and are basic in character due to the presence of certain metallic oxides such as alkali and alkaline earth metal oxides. These solid effluents are the so-called "under boiler” ashes and bottom ash. Certain bottom clinkers are considered non-toxic under the legislation in force, and can be stored in landfills or used without danger, for example in bitumens, after de-railing. These bottom ash represent approximately 30% by weight of the initial product. Ashes under boilers are very toxic powdery materials because they contain heavy metals and their salts, and must be stored carefully, after being stabilized, in protected sites awaiting possible reprocessing.
- the gaseous effluents are more or less acidic in character due to the presence of acid gases such as HCl and HF and anhydrides of gaseous acids such as S0 and C0 2 , and they include toxic compounds such as heavy metals and their salts, and solid residues from incineration also called fly ash.
- acid gases such as HCl and HF and anhydrides of gaseous acids such as S0 and C0 2
- toxic compounds such as heavy metals and their salts
- solid residues from incineration also called fly ash.
- These gaseous or smoke effluents must be filtered and treated to neutralize their acidity, to condense metals and their salts, and to retain fly ash before being released into the atmosphere. For example, the wet neutralization of these effluents leads to the formation of a more or less agglomerated pulverulent or particulate material called "filtration cake".
- the fly ash and filter cake set constitutes a residue from the purification of household waste incineration fumes, also called REFIOM. It constitutes approximately 3% by weight of the initial waste.
- the composition of REFIOMs is very variable and depends on the techniques for cleaning the smoke and the incineration processes used. The following orders of magnitude can be retained for essential constituents in% by weight: calcium 10 to 30%, chlorine 10 to 25%, sulfate 15 to 25%, silicon 3 to 15%, aluminum 2 to 6%, potassium 1 to 7 %, sodium 1 to 4%, metals represent 3 to 4%.
- the polluting fraction which is essentially constituted by heavy metals therefore represents approximately 4% by weight of the total mass of REFIOM.
- the heavy metals the most commonly encountered are zinc, lead, cadmium, nickel and chromium.
- the REFIOMs and the ashes under boilers previously described constitute materials currently considered as "ultimate waste”.
- the metallic salts of these wastes, the heavy metals and their salts are soluble in water and can be easily washed away by rainwater and be dispersed in soils and groundwater.
- Vitrification appears to be the safest way at present to inert these final incineration materials or waste, for storage or even recovery. Indeed, these materials, which contain silica and alumina liquefy and form a fusion bath when subjected to temperatures above 1300 ° C. This molten bath when cooled forms a crystalline material or a solid amorphous glass, a true heavy metal retention matrix.
- vitrification processes generally lead to the use of flux additives such as boron oxide, sodium oxide, potassium oxide and / or network forming oxides such as silica which is most commonly used. These products often have the disadvantage of being expensive. On the other hand, all the elements present in these effluents are not digestible in the glass, which causes phase demixing.
- vitrification processes do not generally accept waste in liquid or liquid-solid suspension form due to the high gassing produced during melting. This implies the installation, upstream of the vitrification process, of drying equipment such as filters or calciners.
- the object of the present invention is in particular to overcome the aforementioned drawbacks and to reduce the overall flow of solid residues to be placed in landfill, by providing a process and a device for treating and conditioning an effluent comprising salts of heavy metals. .
- the process of the invention is characterized in particular in that it comprises in this order: a) heating of the effluent to be treated so as to make the anions and cations of the salts gaseous volatile heavy metals which it contains and to evacuate them from the heated effluent, b) a step of recovery of the gaseous products resulting from the heating of the effluent, said gaseous products including the anions and cations of the volatile heavy metal salts, evacuated by heating the effluent, c) a step of treating said recovered gaseous products so as to isolate the heavy metals which they contain in a digestible chemical form in a vitrification matrix, d) a step of reintroducing said heavy metals , in said digestible chemical form, in the heated effluent of step a), to obtain a vitrifiable effluent, and optionally e) a vitrification step of the vitrifiable effluent.
- the effluent can be one of those mentioned above.
- the method of the invention makes it possible to treat effluents from methods of surface treatment by chemical means, from method of incineration of household waste, or from any other method generating effluents comprising salts of heavy metals.
- the metals can be, for example, those mentioned above. They form the cations of heavy metal salts.
- Step a) of the process of the present invention can be carried out for example in a melting furnace used for the melting of the abovementioned effluents. It makes it possible to make gaseous in particular the anions and cations of the volatile heavy metal salts contained in the effluent to be treated, and thus to evacuate, or distill, under the effect of heating, these heavy metal salts. It also makes it possible to remove the anions from these salts which are, for example of the chloride, fluoride, P0 " , S0 4 ⁇ , etc. type, that is to say those which may be present in the effluents defined above. above .
- This stage of the process makes it possible to distill almost all of the heavy metals present in the effluent to be treated, and also to eliminate in particular the chloride anions present in certain effluents, in order to make the fraction of the effluent remaining in the oven vitrifiable. , that is to say the non-volatile fraction at the heating temperature chosen for this step.
- a preliminary dechlorination treatment was necessary. The absence of such preliminary treatment resulted in the departure of almost all of the heavy metals in gaseous form which would not allow their incorporation into the vitreous matrix.
- vitrification requires compliance with a number of criteria.
- ⁇ ) The elements must be digestible in the glass so as to avoid the unmixed phases or the precipitates in large quantities.
- the aforementioned anions are thus the most troublesome elements due to their poor solubility in glass which causes phase demixing.
- the materials obtained are then non-homogeneous and of poor quality, the molten salt phase which is not vitrified extracting a non-negligible proportion of toxic cations.
- these phases being lighter than glass, the fairly high volatility of the salts is further exacerbated by their contact with the gaseous atmosphere.
- Waste, glass and its by-products must be compatible with the technological materials used for the parts of the oven in contact with them. Indeed, the anions Cl " and S0 4 2 ⁇ in particular can be aggressive vis-à-vis certain refractories.
- the process of the present invention has the advantage of being free from this preliminary treatment since the chlorides are eliminated during step a) of heating the effluent, and that of being able to incorporate the heavy metals into the vitreous matrix by example from the heating of the effluent.
- the process of the present invention makes it possible in particular to eliminate the anions Cl " and S0 4 ⁇ and to provide a vitrifiable effluent meeting the above criteria.
- step a) also makes it possible to evacuate the liquid phase in the form of vapors or mist recovered with the aforementioned gaseous products.
- liquids can for example be water, organic solvents, etc. The amount of water present is only limiting by the overconsumption of energy which it induces for its evaporation.
- the heating can be carried out for example in several stages, or gradually, to first evacuate the liquid phase of the effluent so as to obtain a solid residue. This solid residue can then be heated to a temperature sufficient to remove the heavy metal salts which it contains.
- Heavy metal salts are volatile from around 1000 ° C.
- the heating temperature of the effluent is preferably at least at this temperature.
- the effluent, or the residue can be heated until it melts, that is to say to the vitrification temperatures.
- the heating temperature in this step also depends on the nature of the effluent, it can for example be from 1200 ° C. to temperatures above 1500 ° C. for effluents such as those mentioned above. In addition, the heating temperature may depend on the possible addition of vitrification additives to the heated effluent as set out below.
- the heating can be carried out by means of an energy source which can be for example plasma, arc plasma, resistance or induction.
- the combustion of any fuels contained in the treated effluents can contribute to the heating of the effluent.
- step b) the gaseous products from step a) of heating are recovered.
- the recovery of these gaseous products including the anions and cations of the heavy metal salts can be done by a pipe allowing a collection of gases and fumes from the oven.
- These gaseous products are preferably maintained at a sufficient temperature, generally at 400 ° C. or more, to avoid condensation of the volatile heavy metal salts which they contain, until the stage of treatment of said gaseous products.
- Step c) of treatment of the recovered gaseous products can for example comprise a first washing of the gaseous products so as to block the heavy metal salts in a solution, a precipitation of the metals in a digestible chemical form in a vitrification matrix, a filtration, and possibly a second washing of heavy metals in said digestible form.
- the first washing allows the gaseous metal salts from the oven to be dissolved or blocked, and recover all the soluble fraction containing all the metals. Washing can for example be carried out in a gas / liquid reactor, or in a packed tower or any other equipment making it possible to perform this function.
- this operation is carried out with water.
- the solution obtained with this washing is more or less acidic depending on the initial composition of the solid or effluent residue treated.
- This solution can then be adjusted in acidity in a precipitation apparatus of the ripener-thickener type to precipitate the metals in a digestible chemical form in a glass matrix and preferably insoluble in water, for example in the form of metal carbonate, for example by means of sodium carbonate or calcium carbonate.
- metal carbonates are insoluble. This chemical form, which is digestible in a glass matrix, is suitable for vitrification. In this example, it may be powdered sodium carbonate or in solution at 200 g / l, or powdered calcium carbonate. These precipitate quantitatively the metals and very particularly the most troublesome such as cadmium, nickel, lead and zinc.
- the precipitation can be carried out for example at a pH of less than about 10, for example between 8 and 10, for example at a pH of 9. This makes it possible in particular to limit the redissolution of the aluminum and chromium oxides which may be present in these gaseous products.
- the precipitation can be carried out hot, for example at a temperature ranging from approximately 40 to approximately 60 ° C., for example at approximately 50 ° C., which increases the rate of formation and of maturation of the precipitate and makes it possible to avoid the untimely precipitation of lead chloride for certain effluents.
- the precipitate obtained can be filtered, for example, on a continuous filter of the rotary or belt type, or any other equivalent equipment, and optionally undergo a second washing during filtration, for example with water.
- the filtration water can be recovered and concentrated by evaporation, which allows, on the one hand, to recover water usable for the first washing of the gases from the melting furnace and for the second washing during filtration during step c), and, on the other hand, recovering the alkaline and alkaline earth salts.
- This embodiment makes it possible, on the one hand, to separate the polluting metals from a complex effluent, and to make them vitrifiable with a view to their storage, and, on the other hand, to recover inert salts with respect to the environment and usable for example in road engineering.
- This embodiment also has the advantage of allowing recycling of the water inside the treatment unit.
- stage d the washed precipitate, that is to say the heavy metals in a digestible chemical form in a vitrification matrix, is reintroduced into the heated effluent of stage a) free of metal salts heavy.
- the salts of metals have been precipitated as carbonates, the metal carbonates decompose into metal oxides with emission of carbon dioxide.
- the heating step a) can be carried out in a first chamber
- the step d) can be carried out in a second chamber, the first and the second chambers being separated, a passage being provided between the two chambers so that the heated effluent can pass from the first to the second chamber when it is free of volatile heavy metal salts.
- the introduction of the metals in the digestible chemical form into a glass matrix in the second chamber makes it possible to avoid possible recombinations of the metals, for example with the chlorine present in the gaseous emissions from the heating of the effluent from step a), in the first chamber.
- steps a) and d) can be carried out in a single heating and melting chamber for vitrification of the treated effluent.
- the implementation of the method of the invention can be used to recover metals in a digestible chemical form in a glass matrix after treatment of sludges containing metal salts for later use such as recovery of a recoverable metal, for example chromium, copper, etc.
- the furnace chamber can be with a separate atmosphere. This mode of embodiment is shown diagrammatically in FIG. 4 and explained in the examples below.
- step e) the effluent assembly free of volatile heavy metal salts contained in the furnace and metals in said digestible chemical form in a glass matrix, called vitrifiable effluent, is vitrified.
- vitrifiable effluent some effluents require the addition of a vitrification additive for this, others do not.
- This step e) is intended to render these treated effluents inert by trapping them in a glass matrix which can be stored safely. It is optional. Indeed, the treated effluent and the metals in said digestible chemical form can be stored, or put on standby, before proceeding to their vitrification or to be used for other purposes.
- step e) of vitrification can be carried out in said oven.
- a vitrification additive can be added to the effluent, for example in the case where the effluent does not include, or not enough, fluxes or oxides forming endogenous networks allowing its vitrification.
- This additive can be one of those known to those skilled in the art.
- the average composition of a common industrial glass is as follows: Vitrifying Si0 2 + B 2 0 3 + Al 2 0 3 72 to 74% by weight
- the vitrification additive includes these elements and is added, if necessary, to the effluent to be vitrified in an amount sufficient to reach the abovementioned percentages.
- the amount of additive can range, for example, up to 90% by weight of the mixture comprising the additive and the effluent to be treated.
- REFIOMs can have a high concentration of silica, the main component of glass, of the order of 30 to 35% by weight. They therefore do not necessarily require the addition of vitrification additives.
- This additive can be added to any process step of the invention when necessary.
- the heating of the effluent can be adapted in particular according to the presence of additive.
- the melting temperature can be between 1200 ° C. and 1350 ° C., preferably around 1300 ° C. Without additive, the melting temperature can be higher than 1500 ° C and the volatile metals are largely released.
- the process can be carried out in a "batch" system, or continuously.
- the invention also relates to a device for implementing the method of the present invention, said device comprising:
- An oven for heating the effluent to be treated comprising a heating means, a means for entering the effluent to be treated into the oven, a means for recovering the products gaseous from the heating of the effluent to be treated in the oven, and a means for removing the treated effluent from the oven,
- a means for treating the recovered gaseous products, and isolating the heavy metals in a digestible chemical form in a vitrification matrix said means for treating gaseous products being connected with the means for recovering these products from the oven, and a means for reintroduction into the furnace of heavy metals in said digestible chemical form in the heated effluent free of heavy metal salts.
- the heating means may for example be one of those mentioned above.
- the means for entering the effluent to be treated makes it possible to introduce the effluent into the oven and the means for discharging the treated effluent makes it possible to evacuate the treated effluent, possibly vitrified from the oven.
- these inlet and outlet means can be regulated so as to optimize the process of the present invention.
- the means for recovering the gaseous products from the heating of the effluent can for example be one of those mentioned above, for example a pipe. It may further comprise a system for maintaining the temperature of the gaseous products, for example a heat-insulating system, a system for heating the pipes, in-line heat exchangers, etc., so as to maintain the gaseous products at a temperature sufficient to limit the condensation of volatile metals between the oven and the means for treating gaseous products.
- a system for maintaining the temperature of the gaseous products for example a heat-insulating system, a system for heating the pipes, in-line heat exchangers, etc.
- the means for recovering gaseous products is connected with the means for treating these products.
- the means for treating gaseous products and isolating heavy metals can be one of the above. It can comprise, for example, a precipitation apparatus, for example of the ripener-precipitator type, and a filter, for example a continuous filter, for example of the rotary or belt type.
- the oven as described above, can be separate chambers or a single chamber.
- the device comprises an oven with separate chambers as described above allowing primary treatment of the effluent to be vitrified in the first chamber with departure of the volatile heavy metals, and then the addition 1 incorporation in the glass for example of heavy metal carbonates in the second chamber.
- the oven is with a separate atmosphere as described in FIG. 4 and in the examples.
- the means for reintroducing metals in a digestible form into the furnace, in the heated effluent free of heavy metal salts is preferably connected to the second chamber of the furnace.
- the installation comprises a single chamber melting furnace allowing the treatment primary of the effluent to be vitrified and the simultaneous incorporation into glass of heavy metals in a digestible chemical form in a glass matrix, for example in the form of carbonates of heavy metals.
- the means for reintroducing heavy metals in said digestible chemical form can be constituted, for example, by a screw, belt, vibration, etc. conveyor.
- the device according to the invention may further comprise an evaporation system for concentrating the washing water from the treatment of gaseous products.
- FIG. 1 is a diagram illustrating the steps of the method of the present invention according to the first embodiment, that is to say in which steps a) and d) are carried out in two separate chambers,
- FIG. 2 is a diagram illustrating the steps of the method of the present invention according to the second embodiment, that is to say in which steps a) and d) are carried out in a single chamber,
- FIG. 3 is a diagram illustrating an oven usable in the second embodiment of the present invention
- - Figure 4 is a diagram illustrating an oven usable in the third embodiment of the present invention.
- Example 1 Device for implementing the method of the invention according to the first embodiment As illustrated in FIG. 1, the device comprises six chemical equipments, referenced F and 2 to 5, adapted to the different steps of the method of 1 invention.
- It includes a melting furnace F for heating the effluent to be treated, comprising two chambers 1 and 1 ′ of separate atmospheres, the total volume and the heating power of which are adaptable to the flow rate of ffluent to be treated, the liquid effluents or solids being introduced continuously by the inlet means 11 of the effluent to be treated in the chamber 1 of the furnace F.
- Reference 13 indicates a supply line for vitrification additive.
- a means 15, 17 in the form of a pipe, for recovering the gaseous products resulting from the heating of the effluent, allows the collection of the gaseous products formed during step a) of the process containing the volatile metals and the fumes. It includes a temperature maintenance system 6 for the gaseous products collected which makes it possible to maintain the temperature of these products and fumes in line 21 supplying the means T for processing the recovered gaseous products.
- This means T comprises a system 2 for purifying the fumes, a line 22 for extracting the purified gaseous residues and directing them towards the atmosphere, a line 23 for the arrival of a smoke washing solution, a line 24 making it possible to collect the smoke washing solution to direct it to a system 3 for precipitation / washing of metals in their digestible chemical form in a glass matrix.
- a reagent intended to transform the heavy metals into a digestible chemical form in a glass matrix for example a sodium or calcium carbonate, is introduced via line 31 into the system 3.
- a pipe 32 makes it possible to collect the heavy metals in said digestible form, generally in the form of a precipitate, from the system 3 to direct them to a system 4 for filtration / washing of the metals in their digestible chemical form.
- the mother liquors for filtration and washing are collected via a pipe 41 for recycling.
- the heavy metals in said digestible form are reintroduced via line 12 into the effluent free of heavy metal salts present in the chamber 1 'and coming from chamber 1.
- FIG 4 is a diagram of an oven (II) usable in the third embodiment of the present invention.
- This oven (II) has a separate atmosphere or partitioned sky. Indeed, it includes a partition 56 which prevents fogging and volatile metals are in contact with the part of the furnace in which the heavy digestible metals are reintroduced into the effluent.
- This oven (II) is provided with the lines 11, 12, 13, 14, 15 and 16 mentioned above.
- the reference 54 indicates a heating means and the reference E the molten effluent.
- the heavy metals are in the form of carbonates of digestible heavy metals in a glass matrix
- the heavy metals when they are reintroduced into the effluent free of heated heavy metal salts, there is emission of fumes of dioxide of carbon.
- a pipe 16 makes it possible to collect this smoke, and to lead them into the pipe 17.
- a line 14 allows the continuous elimination of the solidified glasses and products formed in the furnace F towards a discharge Dl. This oven allows continuous discharge of the vitrified product.
- the mother liquors for filtration and washing are collected from the system 4 by a line 41 which ensures their elimination or their orientation towards an optional system 5 for evaporation and concentration of these mother liquors.
- Example 2 Device for implementing the method of the invention according to the second embodiment
- FIGS. 2 and 3 This second embodiment is shown diagrammatically in FIGS. 2 and 3.
- the references identical to those of FIG. 1 indicate the same things.
- the furnace (I) consists of a single chamber I whose volume and heating power are adapted to the flow of effluent to be treated. Solid or liquid effluents are introduced through line 11 into the furnace. A line 12 allows the heavy metals to be reintroduced in the digestible chemical form into the furnace F '. Reference 13 indicates an inlet pipe for a vitrification additive. A pipe 15 collects the fumes and brings them to the system for treating, or purifying, gaseous products.
- a single chamber furnace (I) is shown diagrammatically in FIG. 3 in which the furnace 1 is provided with the lines 11, 12, 13, 14 and 15 mentioned above. It includes a heating means 54. The molten effluent is referenced E.
- a REFIOM is treated in a direct induction furnace in a cold crucible, without adding any additive.
- the heating temperature was about 1600 ° C.
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Abstract
Description
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001541627A JP2003515448A (ja) | 1999-11-29 | 2000-11-28 | 排出物をガラス化のために処理調整する方法及び装置 |
EP00985342A EP1250197A1 (fr) | 1999-11-29 | 2000-11-28 | Procede et dispositif de traitement et de conditionnement d'un effluent en vue d'une vitrification |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9914991A FR2801521B1 (fr) | 1999-11-29 | 1999-11-29 | Procede et dispositif de traitement et de conditionnement d'un effluent en vue d'une vitrification |
FR99/14991 | 1999-11-29 |
Publications (1)
Publication Number | Publication Date |
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WO2001039902A1 true WO2001039902A1 (fr) | 2001-06-07 |
Family
ID=9552646
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR2000/003319 WO2001039902A1 (fr) | 1999-11-29 | 2000-11-28 | Procede et dispositif de traitement et de conditionnement d'un effluent en vue d'une vitrification |
Country Status (4)
Country | Link |
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EP (1) | EP1250197A1 (fr) |
JP (1) | JP2003515448A (fr) |
FR (1) | FR2801521B1 (fr) |
WO (1) | WO2001039902A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2228146A1 (fr) * | 2009-03-13 | 2010-09-15 | Kalogeo Anlagenbau GmbH | Conditionnement thermique de cendres |
EP2650391A1 (fr) * | 2012-04-13 | 2013-10-16 | Andritz Energy & Environment GmbH | Procédé d'inertisation de métaux lourds tels que p. ex. le chrome hexavalent, de chlorures et d'autres halogènes ainsi que de solides solubles et de contaminations métalliques |
WO2024040686A1 (fr) * | 2022-08-25 | 2024-02-29 | 北京大学深圳研究生院 | Verre-mère et procédé et système d'utilisation cyclique pour élément de métal alcalin dans du verre-mère |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5041398A (en) * | 1989-02-22 | 1991-08-20 | Wheaton Industries | Method for treating incinerator ash |
FR2717249A1 (fr) * | 1994-03-14 | 1995-09-15 | Speic | Procédé et installation d'épuration de fumées issues d'un incinérateur à fusion et vitrification des déchets. |
US5462570A (en) * | 1993-01-26 | 1995-10-31 | Dunkirk International Glass And Ceramics Corporation | Process for producing an environmentally acceptable abrasive product from hazardous wastes |
FR2719793A1 (fr) * | 1993-07-30 | 1995-11-17 | Cnim | Procédé de vitrification de résidus solides issus de l'incinération de déchets ménagers et/ou industriels, dispositif pour la mise en Óoeuvre de ce procédé et produit issu de ce procédé. |
FR2721237A1 (fr) * | 1994-06-15 | 1995-12-22 | Commissariat Energie Atomique | Procédé de traitement et de conditionnement d'effluents solides ou liquides chargés en métaux lourds. |
FR2726492A1 (fr) * | 1994-11-09 | 1996-05-10 | Electricite De France | Adjuvant et procede pour la stabilisation des dechets contenant des elements metalliques |
-
1999
- 1999-11-29 FR FR9914991A patent/FR2801521B1/fr not_active Expired - Fee Related
-
2000
- 2000-11-28 EP EP00985342A patent/EP1250197A1/fr not_active Withdrawn
- 2000-11-28 JP JP2001541627A patent/JP2003515448A/ja active Pending
- 2000-11-28 WO PCT/FR2000/003319 patent/WO2001039902A1/fr not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5041398A (en) * | 1989-02-22 | 1991-08-20 | Wheaton Industries | Method for treating incinerator ash |
US5462570A (en) * | 1993-01-26 | 1995-10-31 | Dunkirk International Glass And Ceramics Corporation | Process for producing an environmentally acceptable abrasive product from hazardous wastes |
FR2719793A1 (fr) * | 1993-07-30 | 1995-11-17 | Cnim | Procédé de vitrification de résidus solides issus de l'incinération de déchets ménagers et/ou industriels, dispositif pour la mise en Óoeuvre de ce procédé et produit issu de ce procédé. |
FR2717249A1 (fr) * | 1994-03-14 | 1995-09-15 | Speic | Procédé et installation d'épuration de fumées issues d'un incinérateur à fusion et vitrification des déchets. |
FR2721237A1 (fr) * | 1994-06-15 | 1995-12-22 | Commissariat Energie Atomique | Procédé de traitement et de conditionnement d'effluents solides ou liquides chargés en métaux lourds. |
FR2726492A1 (fr) * | 1994-11-09 | 1996-05-10 | Electricite De France | Adjuvant et procede pour la stabilisation des dechets contenant des elements metalliques |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2228146A1 (fr) * | 2009-03-13 | 2010-09-15 | Kalogeo Anlagenbau GmbH | Conditionnement thermique de cendres |
EP2650391A1 (fr) * | 2012-04-13 | 2013-10-16 | Andritz Energy & Environment GmbH | Procédé d'inertisation de métaux lourds tels que p. ex. le chrome hexavalent, de chlorures et d'autres halogènes ainsi que de solides solubles et de contaminations métalliques |
WO2024040686A1 (fr) * | 2022-08-25 | 2024-02-29 | 北京大学深圳研究生院 | Verre-mère et procédé et système d'utilisation cyclique pour élément de métal alcalin dans du verre-mère |
Also Published As
Publication number | Publication date |
---|---|
FR2801521A1 (fr) | 2001-06-01 |
FR2801521B1 (fr) | 2002-04-26 |
EP1250197A1 (fr) | 2002-10-23 |
JP2003515448A (ja) | 2003-05-07 |
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