CA2141575A1 - Process for disposing of sodium-sulphur accumulator cells - Google Patents
Process for disposing of sodium-sulphur accumulator cellsInfo
- Publication number
- CA2141575A1 CA2141575A1 CA 2141575 CA2141575A CA2141575A1 CA 2141575 A1 CA2141575 A1 CA 2141575A1 CA 2141575 CA2141575 CA 2141575 CA 2141575 A CA2141575 A CA 2141575A CA 2141575 A1 CA2141575 A1 CA 2141575A1
- Authority
- CA
- Canada
- Prior art keywords
- process according
- sulfur
- sodium
- solution
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title claims description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 210000004027 cell Anatomy 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 210000000352 storage cell Anatomy 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000011593 sulfur Substances 0.000 claims description 31
- 229910052717 sulfur Inorganic materials 0.000 claims description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- 238000000909 electrodialysis Methods 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims 3
- 239000011343 solid material Substances 0.000 claims 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 238000012958 reprocessing Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 3
- 229920001021 polysulfide Polymers 0.000 abstract description 2
- 239000005077 polysulfide Substances 0.000 abstract description 2
- 150000008117 polysulfides Polymers 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 229960005349 sulfur Drugs 0.000 description 22
- 235000001508 sulfur Nutrition 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 13
- 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 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229940083608 sodium hydroxide Drugs 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 244000201986 Cassia tora Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 229910014103 Na-S Inorganic materials 0.000 description 1
- 229910014147 Na—S Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- KNSPATVVQHLSKI-UHFFFAOYSA-N cyano thiocyanate;sodium Chemical compound [Na].N#CSC#N KNSPATVVQHLSKI-UHFFFAOYSA-N 0.000 description 1
- -1 hydrogen - Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NCAIGTHBQTXTLR-UHFFFAOYSA-N phentermine hydrochloride Chemical compound [Cl-].CC(C)([NH3+])CC1=CC=CC=C1 NCAIGTHBQTXTLR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/16—Hydrogen sulfides
- C01B17/165—Preparation from sulfides, oxysulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/20—Preparation by reacting oxides or hydroxides with alkali metal salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Electrochemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
- Fertilizers (AREA)
Abstract
A B S T R A C T
Sodium-sulfur storage cells are disposed of and recycled by crushing the cells in the presence of water, by separating the solid residual materials and by preparing an aqueous solution of Na-polysulfide; variations in the reaction pro-cess allow the products thus obtained to be economically processed while minimizing secondary products.
Sodium-sulfur storage cells are disposed of and recycled by crushing the cells in the presence of water, by separating the solid residual materials and by preparing an aqueous solution of Na-polysulfide; variations in the reaction pro-cess allow the products thus obtained to be economically processed while minimizing secondary products.
Description
i~ ~ S7~ , ~
PROC13SS E'O~ DISPOSING OF SODI~ SULF~7R STORAGE: CEI~I~S .
The invention relates to a ~roces~ for di~osing of sodium-sulfur ~tora~e cells.
Increasing coneum~tion o~ sodium-~ulfur storage cells crea- ~ ~ ;
tes the ~eed to re~rocess these storage cells and to reproce~s or recycle the com~onents o~ the cell.
It is kn~wn, accordi~g to the German unexamined }aid-o~en ~ ;
~aten~ application 39 27 225, to embed ~torage cells in wax-like materials such as ~araffin, remove the sodium by way of fusing, and ~e~erately remove and recycle the sulfur electrodes and the casing materials.
Further, it is known from ~uropean patent a~licat~on ~ ~
0 433 654 to shred the cells and, by adding sodium cyaniae ;~`
and water, produce sodium thiocyanide.
',` ' It i~ an ob~ect of the invention to ~rocess sodium-sulfur storage cells by em~loying simple mQthods and means to .
yield maximum ~ro~ortions of useful and recyclable substan~
ces .
The object is achieved according to the features of Claim 1 hereinbelow.
The followin~ variants ~resent themselves in accordance with this invention~
Variant 1: `
The battery or individual cells are mechanically crushed or disinte~rated by shredding or similar techni~ues. In order to ~revent oxidation from occurring, this process may be carried out under inert qas or vacuum, or, preferably, --~
under water. ~he use of water ~resents the ad~antage that -~
PROC13SS E'O~ DISPOSING OF SODI~ SULF~7R STORAGE: CEI~I~S .
The invention relates to a ~roces~ for di~osing of sodium-sulfur ~tora~e cells.
Increasing coneum~tion o~ sodium-~ulfur storage cells crea- ~ ~ ;
tes the ~eed to re~rocess these storage cells and to reproce~s or recycle the com~onents o~ the cell.
It is kn~wn, accordi~g to the German unexamined }aid-o~en ~ ;
~aten~ application 39 27 225, to embed ~torage cells in wax-like materials such as ~araffin, remove the sodium by way of fusing, and ~e~erately remove and recycle the sulfur electrodes and the casing materials.
Further, it is known from ~uropean patent a~licat~on ~ ~
0 433 654 to shred the cells and, by adding sodium cyaniae ;~`
and water, produce sodium thiocyanide.
',` ' It i~ an ob~ect of the invention to ~rocess sodium-sulfur storage cells by em~loying simple mQthods and means to .
yield maximum ~ro~ortions of useful and recyclable substan~
ces .
The object is achieved according to the features of Claim 1 hereinbelow.
The followin~ variants ~resent themselves in accordance with this invention~
Variant 1: `
The battery or individual cells are mechanically crushed or disinte~rated by shredding or similar techni~ues. In order to ~revent oxidation from occurring, this process may be carried out under inert qas or vacuum, or, preferably, --~
under water. ~he use of water ~resents the ad~antage that -~
- 2 - ~-'`' '.'~'"' `,'`''',' it is ~ossible to intercept the exothermic reaction o~ any sodium metal which may possibly still be present, thus ~ut- ~`
ting less stre~s on the comminutins~ device, e.~. the shred-der. In addition, the dissol~ing ~roce8~ i~ already set off while the disintegrat~on takes ~la~:e, thereby ~aving time.
Hydrogen resulting from the above ~rocess may be em~loyed ~or heating ~urpo~es. The disintegration should result in pieces of 0.1 cm to 5 cm, ~referably about 1 cm.
The dissolution reaction of the ~olysulfide and the solid sulfur may take ~lace within a temperature inter~al from ~ ~-room tem~erature to 200 C, ~referably the reaction i8 car-ried out at 120 C. De~ending on the ty~e of battery, the dissolution réaction does generally not require the addition of chemicals, such as a lye. By adding an oxidant ` ;~
subsequent to dissolution, the entire amount of ~oly-~ulfide, which has been formed from the solid sulfur, can generally be oxidated to sulfate without transferring the solution to another reactor. Pre~exably, hydrogen ~eroxide is u~ed for the oxidat~on proce~s. To achieve complete con-~er~ion, the ~H must always be maintained above ~H 8. To this end a lye i~ u~ed, preferably sodium hydroxide. After ~e~arating the liquid, the residue is washed with water.
The re~ulting washings are used in the dissol~ing ~roces~
Th~ cleaned solids may be se~arated into metals and non~
metals if recycling the components is economically feas-ible. Otherwise, un~roblematic waste dis~osal i~ possible, ~or example, on a dum~ing ground. The salt ~olution may be dis~o~ed o~ or reused either immediately or after eva~orat-ing, the resulting water being reintroduced into the wash-ing or dissol~ing ~roce~s.
Variant`2:
The disintegration, dissolution and se~aration ~rocesses, - `~
like the treatment of the solid re~idue, are carried out as described under 1.
4 ~. 5 7 j' ' ' ;, ~
ting less stre~s on the comminutins~ device, e.~. the shred-der. In addition, the dissol~ing ~roce8~ i~ already set off while the disintegrat~on takes ~la~:e, thereby ~aving time.
Hydrogen resulting from the above ~rocess may be em~loyed ~or heating ~urpo~es. The disintegration should result in pieces of 0.1 cm to 5 cm, ~referably about 1 cm.
The dissolution reaction of the ~olysulfide and the solid sulfur may take ~lace within a temperature inter~al from ~ ~-room tem~erature to 200 C, ~referably the reaction i8 car-ried out at 120 C. De~ending on the ty~e of battery, the dissolution réaction does generally not require the addition of chemicals, such as a lye. By adding an oxidant ` ;~
subsequent to dissolution, the entire amount of ~oly-~ulfide, which has been formed from the solid sulfur, can generally be oxidated to sulfate without transferring the solution to another reactor. Pre~exably, hydrogen ~eroxide is u~ed for the oxidat~on proce~s. To achieve complete con-~er~ion, the ~H must always be maintained above ~H 8. To this end a lye i~ u~ed, preferably sodium hydroxide. After ~e~arating the liquid, the residue is washed with water.
The re~ulting washings are used in the dissol~ing ~roces~
Th~ cleaned solids may be se~arated into metals and non~
metals if recycling the components is economically feas-ible. Otherwise, un~roblematic waste dis~osal i~ possible, ~or example, on a dum~ing ground. The salt ~olution may be dis~o~ed o~ or reused either immediately or after eva~orat-ing, the resulting water being reintroduced into the wash-ing or dissol~ing ~roce~s.
Variant`2:
The disintegration, dissolution and se~aration ~rocesses, - `~
like the treatment of the solid re~idue, are carried out as described under 1.
4 ~. 5 7 j' ' ' ;, ~
.: ~ ..'':
The solution i~ reacted with acid, ~referably sulfuric acid, and oxidant, ~referably hydrogen ~eroxide. The reac- f~
t~on tem~exature may be between room temperature and 150 C, and, ~refereably, at the end of the exothermal reaction, a~roximately 120 C. This yields elementary sul-~ur. The hydro~en sulfide whlch ha8 been formed i~ o~idize in situ to ~ul~ata. If the tem~erature i8 maintained above the meltin~ ~oint of sulfur, a liquid sulfur phase quic~ly form~, which can be easily decanted as a liquid, purified ~
and recycled. The disposal of the solution and solids iB - `. ,~ ~, carried out a~ describea under 1. ;
variant 3:
~he size-reduction, dissolution an~ se~aration proces~es, like the treatment o~ the solid residue, are carried out as described under 1.
The solution is treated with acid, ~referably sulfuric acid. This ~rocess yields sulfur, which is decanted as in 2. ~ydrogen sulfide which has formed simultaneously 18 withdrawn, decocted or stripped with gas, preferably nitro~en. It is used as a chemical or it is con~erted to further sul~ur in a Claus process plant. Optionally, the purification of this sulfur takes place together with the decanted sulfur.
The salt solution and the solids are dis~osea of as in 1.
, - . ~
The variants are shown in the form of diagrammes in Figures 1 to 3.
- . -The ~roce~s variants have in common that initially the storage cells are ~isinte~rated in the ~resence of water and the soluble com~onents of the electric element are di~
solved to form a sodium-~olysulfide solution. Either simul~
taneously or subsequent thereto, ~referably sodium hydrox-ide solution or sulfuric acid is added, which leads to the 7 ~ ~:
The solution i~ reacted with acid, ~referably sulfuric acid, and oxidant, ~referably hydrogen ~eroxide. The reac- f~
t~on tem~exature may be between room temperature and 150 C, and, ~refereably, at the end of the exothermal reaction, a~roximately 120 C. This yields elementary sul-~ur. The hydro~en sulfide whlch ha8 been formed i~ o~idize in situ to ~ul~ata. If the tem~erature i8 maintained above the meltin~ ~oint of sulfur, a liquid sulfur phase quic~ly form~, which can be easily decanted as a liquid, purified ~
and recycled. The disposal of the solution and solids iB - `. ,~ ~, carried out a~ describea under 1. ;
variant 3:
~he size-reduction, dissolution an~ se~aration proces~es, like the treatment o~ the solid residue, are carried out as described under 1.
The solution is treated with acid, ~referably sulfuric acid. This ~rocess yields sulfur, which is decanted as in 2. ~ydrogen sulfide which has formed simultaneously 18 withdrawn, decocted or stripped with gas, preferably nitro~en. It is used as a chemical or it is con~erted to further sul~ur in a Claus process plant. Optionally, the purification of this sulfur takes place together with the decanted sulfur.
The salt solution and the solids are dis~osea of as in 1.
, - . ~
The variants are shown in the form of diagrammes in Figures 1 to 3.
- . -The ~roce~s variants have in common that initially the storage cells are ~isinte~rated in the ~resence of water and the soluble com~onents of the electric element are di~
solved to form a sodium-~olysulfide solution. Either simul~
taneously or subsequent thereto, ~referably sodium hydrox-ide solution or sulfuric acid is added, which leads to the 7 ~ ~:
- 4 - ~
.
formation, either com~letely or ~artially, of sodium 8ul-fate. The ~tructural ~arts o~ the cell, i.e. the cell wall, electrode~, ceramicR, etc. can be se~arated at a~y time a~
soon a~ the Na-~olysulfide has been d~ssolvea.
The amount of sodium sulfate formed can be increased by adding aqueou~ h~dro~en peroxide ~olutio~.
Hydroge~ sul~ide i8 reacted with ~I202-solution to form sul-fur and~or ~ulfate. This can yield ~odium salt as a uni~orm ~roduct, which may be eva~orated, o~tionally ~urified and crystalliz~d in a known manner.
Sulfuric acid together with H202-solution re~uir~s con- ` ~-siderably less ~eroxide as compared to alkalina oxidation and leads to the for~3tion of sodium sulfatQ a~art from elementary sulfur, whereby the sulfur may be se~arated.
Sodium sulfate and sulfur are to be ~urified in a known manner.
....
Sulfuri¢ acid without the addition of ~eroxide rQsults in the formation o~ Na2S0~, sulfur and hydrogen sulfide, the ~ ~
hydrogen sulfide being expulsed and oxidized to elementary ~ ~ -sulfur, for example, in a Claus ~lant. Na2S0~ and the ~rimar~ly formed sulfur may be se~arated as described hereinabove.
Embodiments of the process are ~rovided according to the ~ ~-~ubclaims.
~' The disintegxation o~ batterie~ and inaividual cell~, re-~ectively, often with a content of 40 g ~er individual cell, i~ carried out using breaking or cutting ~lants, advantageously by shredding under water or un~er irrigation with water if ~rovision is made for the inertization of the gas volume. The resulting ~ieces are to have a diameter of 0.1 to 5 cmr ~referably 0.2 to 2 cm. Residues of sodium from cells which have not been com~letely di~char~ed are .. , . ~ . ~ . ........ ...... .
1 5 7 ~ !
~ .
.
formation, either com~letely or ~artially, of sodium 8ul-fate. The ~tructural ~arts o~ the cell, i.e. the cell wall, electrode~, ceramicR, etc. can be se~arated at a~y time a~
soon a~ the Na-~olysulfide has been d~ssolvea.
The amount of sodium sulfate formed can be increased by adding aqueou~ h~dro~en peroxide ~olutio~.
Hydroge~ sul~ide i8 reacted with ~I202-solution to form sul-fur and~or ~ulfate. This can yield ~odium salt as a uni~orm ~roduct, which may be eva~orated, o~tionally ~urified and crystalliz~d in a known manner.
Sulfuric acid together with H202-solution re~uir~s con- ` ~-siderably less ~eroxide as compared to alkalina oxidation and leads to the for~3tion of sodium sulfatQ a~art from elementary sulfur, whereby the sulfur may be se~arated.
Sodium sulfate and sulfur are to be ~urified in a known manner.
....
Sulfuri¢ acid without the addition of ~eroxide rQsults in the formation o~ Na2S0~, sulfur and hydrogen sulfide, the ~ ~
hydrogen sulfide being expulsed and oxidized to elementary ~ ~ -sulfur, for example, in a Claus ~lant. Na2S0~ and the ~rimar~ly formed sulfur may be se~arated as described hereinabove.
Embodiments of the process are ~rovided according to the ~ ~-~ubclaims.
~' The disintegxation o~ batterie~ and inaividual cell~, re-~ectively, often with a content of 40 g ~er individual cell, i~ carried out using breaking or cutting ~lants, advantageously by shredding under water or un~er irrigation with water if ~rovision is made for the inertization of the gas volume. The resulting ~ieces are to have a diameter of 0.1 to 5 cmr ~referably 0.2 to 2 cm. Residues of sodium from cells which have not been com~letely di~char~ed are .. , . ~ . ~ . ........ ...... .
1 5 7 ~ !
~ .
. ' ':'~
rendered harmle~ through water. iHydro~en ~roduced in this ~roce~s can be withdrawn. During comminution the dissolu~
tion reaction o~ the Na-~olysul~ e be~ins and is continued after having been trans~erred to a reactor at temperature~
between room tem~erature and 200C, ~re~erably about 80 to ~;
about 120C, while the liquid is being moved. The dis~olu-tion rate o~ Na-~olysulfide is increasea by elevated tem- ^~
~eratures and in one exam~le is 10 min at 80C. Saturated solutions o~ about 260 g/l with a mean com~osition o~
Na~S2 7 are obtained using water. The dissolution reaction and the sub6equent reactions for recycling the aative sub-stances sod~um/sul~ur are preferably carried out in a reac-tor.
It is ~referred that the reactor be o~ a closed ty~e and ~rovided with a feeding device, gas discharge, bottom drain, heating and stirrer. It is ex~edient to desi~n the reacto~ ~or increased ~ressure of up to 20 bar and for lower ~ressure of. The reaction i~ su~ervised ~refexably by conducti~ity measurements. `~
There are se~eral ~ar~ants for ~he re~rocessing of the Na~
polysulfide solution.
Sodium hydroxide solution with added H202-solution, - ~-advantageously u~ to 30% ~m/m), yields only sodium sulfate.
At temperatures of 80 to 100C the reaction terminates within less than 1 minute. In order to oxidize the sulfur com~letely, 9.1 mol H2O2 ~er mole Na2S27 are necessary, i.e.
a comparatively large amount. This re~rocessing method is ~ -~
thus es~ecially suitable ~or smaller ~lants, all the more ;~ -80 since a~art *rom the reactor no other ~lants are re~
quixed.
The further ~rocessing and recycling, res~ectively, o~ the Na-~olysulfide solution may also be carried out under acidic conditions, pre~erably adding sulfuria acid or, op- -~
tionally, a~ueous hydrochloric acid.
H202 may or may not be added. ~ ;
~ l 4 l ~ ~7 ;~
rendered harmle~ through water. iHydro~en ~roduced in this ~roce~s can be withdrawn. During comminution the dissolu~
tion reaction o~ the Na-~olysul~ e be~ins and is continued after having been trans~erred to a reactor at temperature~
between room tem~erature and 200C, ~re~erably about 80 to ~;
about 120C, while the liquid is being moved. The dis~olu-tion rate o~ Na-~olysulfide is increasea by elevated tem- ^~
~eratures and in one exam~le is 10 min at 80C. Saturated solutions o~ about 260 g/l with a mean com~osition o~
Na~S2 7 are obtained using water. The dissolution reaction and the sub6equent reactions for recycling the aative sub-stances sod~um/sul~ur are preferably carried out in a reac-tor.
It is ~referred that the reactor be o~ a closed ty~e and ~rovided with a feeding device, gas discharge, bottom drain, heating and stirrer. It is ex~edient to desi~n the reacto~ ~or increased ~ressure of up to 20 bar and for lower ~ressure of. The reaction i~ su~ervised ~refexably by conducti~ity measurements. `~
There are se~eral ~ar~ants for ~he re~rocessing of the Na~
polysulfide solution.
Sodium hydroxide solution with added H202-solution, - ~-advantageously u~ to 30% ~m/m), yields only sodium sulfate.
At temperatures of 80 to 100C the reaction terminates within less than 1 minute. In order to oxidize the sulfur com~letely, 9.1 mol H2O2 ~er mole Na2S27 are necessary, i.e.
a comparatively large amount. This re~rocessing method is ~ -~
thus es~ecially suitable ~or smaller ~lants, all the more ;~ -80 since a~art *rom the reactor no other ~lants are re~
quixed.
The further ~rocessing and recycling, res~ectively, o~ the Na-~olysulfide solution may also be carried out under acidic conditions, pre~erably adding sulfuria acid or, op- -~
tionally, a~ueous hydrochloric acid.
H202 may or may not be added. ~ ;
~ l 4 l ~ ~7 ;~
. ' ~
The acidic oxidation with sulfurlc acid and ~202-solu~ion, consumes only one mol~ H2SO~ ~er mole Na2S27, and one mole ~22 under formation of sodi~m sul~ate and sulfur. Tem~era~
tures about of 120C are usable. ~t 120C the sul~ur is able to accumulate at the bottom of t~e reactor and can be arained in liquid form and re~roce~ssed. It i8 of advanta~e that the H202 consum~tion i8 low.
A ~articularly ad~a~ta~eous embodiment with res~ect to minimizing the ~roducts to be withdrawn from the ~rocess, ~ro~ides for the sodium salt to be di~integrated by way of ~;
electrodialysis to form 60dium hydroxido solution ana acid, `~
and, ~referably, to reuse the acid in the ~rocess. ~f Na2SO~ i8 formed it i8 advantageous to carry out a ~reci~
tation with CaO; the resulting gypsum and NaOH can be sup-~lied to a recyclin~ ~rocess or marketed.
~he ac~dic reaction of Na-~oly~ulfide solution may also be `~
effected wlthout the addition of H202 or other oxidants. In this case sodium sulfate, hydrogen sulfide and elementary sulfur i8 ~ormed stoichiometrically. Optionally, hydrogen - ,~
sul~ido may be expulsed at elevated tem~erature with inert gases such as nitrogen, and it may be oxidized in a conven-tional manner with atmos~heric oxygen in a sulfur recovery ~lant to yield sulfur. This variant is suitable for sites with a ~lau~ ~lant and for dis~osing large ~uantities of stora~e cell~. Only one mole H2SO, is consumed ~er mole of Na~S2,7-~xamDle 1:
Alkaline Oxidation 20 g sodium ~olysulfide (0.15 mol calculated as Na2S27) in a~ueous solution is ~laced in a ~res~ure-~roof reactor of : :
~ ~141~7~
.~
The acidic oxidation with sulfurlc acid and ~202-solu~ion, consumes only one mol~ H2SO~ ~er mole Na2S27, and one mole ~22 under formation of sodi~m sul~ate and sulfur. Tem~era~
tures about of 120C are usable. ~t 120C the sul~ur is able to accumulate at the bottom of t~e reactor and can be arained in liquid form and re~roce~ssed. It i8 of advanta~e that the H202 consum~tion i8 low.
A ~articularly ad~a~ta~eous embodiment with res~ect to minimizing the ~roducts to be withdrawn from the ~rocess, ~ro~ides for the sodium salt to be di~integrated by way of ~;
electrodialysis to form 60dium hydroxido solution ana acid, `~
and, ~referably, to reuse the acid in the ~rocess. ~f Na2SO~ i8 formed it i8 advantageous to carry out a ~reci~
tation with CaO; the resulting gypsum and NaOH can be sup-~lied to a recyclin~ ~rocess or marketed.
~he ac~dic reaction of Na-~oly~ulfide solution may also be `~
effected wlthout the addition of H202 or other oxidants. In this case sodium sulfate, hydrogen sulfide and elementary sulfur i8 ~ormed stoichiometrically. Optionally, hydrogen - ,~
sul~ido may be expulsed at elevated tem~erature with inert gases such as nitrogen, and it may be oxidized in a conven-tional manner with atmos~heric oxygen in a sulfur recovery ~lant to yield sulfur. This variant is suitable for sites with a ~lau~ ~lant and for dis~osing large ~uantities of stora~e cell~. Only one mole H2SO, is consumed ~er mole of Na~S2,7-~xamDle 1:
Alkaline Oxidation 20 g sodium ~olysulfide (0.15 mol calculated as Na2S27) in a~ueous solution is ~laced in a ~res~ure-~roof reactor of : :
~ ~141~7~
.~
- 7 - ~
0.5 1 ca~acity. A~ter addi~g 21.8 g (0.54 mol) sodium hy- ;
droxide, 46.2 g (1.36 mol) hydro~en ~eroxide i8 added as 30 ~ (m/m) 801ution while ~tirrinsr. ~he measured conducti- ~`
vity shows that at room term~eratur the reaction terminates ;`~
wit~in 10 to 12 minute~. The react:ion i8 quantitati~e and 53 g (0.4 mol) 80dium sulfate i8 obtained as aqueous 801u-tion.
~:. :,".
~xamDle 2 Acldic Oxidation , ~` ~
,~ ` , ` . ..:
In a reactor a solution of 20 g (0.15 mol) sodium ~oly8ul- ,:
fide i8 ~roduced ~rom used Na-S storage cells by addin~
water and the solid com~one~ts of the cell are removed. `~
While stirrin~ a mixture of 14.7 g (0,15 mol) sulfuric acid ` ``
in 5.1 g (0.15 mol) hydrogen ~eroxide is added as 30 ~
(m/m) solution, Then the closed reactor is heated to 120C.
In this ~rocess the precipitated ~ulfur i8 melted and forms ~ro~let~ which collec~ at the bottom of the reactor. The sul~ur can be removed. 21.5 g (0.15 mol) sodium sulfate and `~
13 g (0.4 mol) sulfur are obtained.
~xam~le 3: -`
Ac~difying and Strip~ing `-A like solution o~ 2Q g sodium ~olysulfide is ~laced in the reactor. 14.7 g (0.15 mol) sulfuric acid is added while stirring. The nascent hydrogen sulfide ga~ is stri~ed ~rom ;~
the reactor with nitrogen and is absorbed in a washing bottle with sodium hydroxide solution. After the reaction has come to an end, the rsactor is heated to 120C internal temperature in order to obtain larger dro~lets. After coo-ling, 8.2 g (0.25 mol) solid sulfur and 21.4 g (0.15 mol) sodium sul~ate is obtained.
The hydxogen sulfide yield i~ 5.1g (0.15 mol).
0.5 1 ca~acity. A~ter addi~g 21.8 g (0.54 mol) sodium hy- ;
droxide, 46.2 g (1.36 mol) hydro~en ~eroxide i8 added as 30 ~ (m/m) 801ution while ~tirrinsr. ~he measured conducti- ~`
vity shows that at room term~eratur the reaction terminates ;`~
wit~in 10 to 12 minute~. The react:ion i8 quantitati~e and 53 g (0.4 mol) 80dium sulfate i8 obtained as aqueous 801u-tion.
~:. :,".
~xamDle 2 Acldic Oxidation , ~` ~
,~ ` , ` . ..:
In a reactor a solution of 20 g (0.15 mol) sodium ~oly8ul- ,:
fide i8 ~roduced ~rom used Na-S storage cells by addin~
water and the solid com~one~ts of the cell are removed. `~
While stirrin~ a mixture of 14.7 g (0,15 mol) sulfuric acid ` ``
in 5.1 g (0.15 mol) hydrogen ~eroxide is added as 30 ~
(m/m) solution, Then the closed reactor is heated to 120C.
In this ~rocess the precipitated ~ulfur i8 melted and forms ~ro~let~ which collec~ at the bottom of the reactor. The sul~ur can be removed. 21.5 g (0.15 mol) sodium sulfate and `~
13 g (0.4 mol) sulfur are obtained.
~xam~le 3: -`
Ac~difying and Strip~ing `-A like solution o~ 2Q g sodium ~olysulfide is ~laced in the reactor. 14.7 g (0.15 mol) sulfuric acid is added while stirring. The nascent hydrogen sulfide ga~ is stri~ed ~rom ;~
the reactor with nitrogen and is absorbed in a washing bottle with sodium hydroxide solution. After the reaction has come to an end, the rsactor is heated to 120C internal temperature in order to obtain larger dro~lets. After coo-ling, 8.2 g (0.25 mol) solid sulfur and 21.4 g (0.15 mol) sodium sul~ate is obtained.
The hydxogen sulfide yield i~ 5.1g (0.15 mol).
Claims (15)
1. A process for the disposal of sodium-sulfur storage cells, characterized in that the storage cells are crushed or disintegrated in the presence of a non-inflammable fluid such as water and/or protective gas or under vacuum and the released chemicals of the cells are processed, while stir-ring, to form an aqueous sodium-polysulfide solution, whereupon the solid materials are separated from the solution, washed with water and are dumped on a dumping ground or supplied to a recycling process, and the solution is disintegrated forming sodium salt, hydrogen sulfide and sulfur.
2. The process according to claim 1, characterized in that nascent hydrogen is collected and, preferably, is used for heating purposes.
3. The process according to claims 1 and 2, characterized in that the solid materials of the cell are separated fol-lowing disintegration or following the formation of the aqueous sodium-polysulfide solution.
4. The process according to one or more of claims 1 to 3, characterized in that the process is carried out within a temperature interval ranging from room temperature to 200°C, and preferably at approximately 120°C.
5. The process according to any one of claims 1 to 4, cha-racterized in that, for recycling, the sodium-polysulfide solution is reacted with lye, preferably sodium hydroxide solution, or with acid, preferably sulfuric acid, optional-ly adding oxidants, particularly H2O2-solution.
6. The process according to claim 5, characterized in that the reaction with sodium hydroxide solution and with H2O2 yields sodium sulfate, whereby the pH value is maintained above pH 8 during the reaction.
7. The process according to claim 5, characterized in that the reaction with H2SO4 and H2O2-solution produces sodium sulfate and sulfur and that the products are subsequently separated.
8. The process according to claim 7, characterized in that the separation of the sulfur is effected by way of heating the solution at least to the melt temperature of elementary sulfur, collecting the sulfur at the bottom of the reactor and draining the sulfur through the bottom valve.
9. The process according to claim 5, characterized in that the reaction with acid, preferably sulfuric acid, yields sodium salt, hydrogen sulfide and sulfur.
10. The process according to one or more of the claims 1 to 9, characterized in that hydrogen sulfide gas which is produced when elementary sulfur is formed is oxidated in situ to sulfate.
11. The process according to claim 9, characterized in that hydrogen sulfide is expulsed and reprocessed, and sulfur is collected and separated.
12. The process according to one or more of claims 1 to 11, characterized in that washing water used in the reproces-sing is, at least for the most part, recycled and is employed when crushing the cells and for dissolving the chemicals, respectively.
13. The process according to one or more of claims 1 to 12, characterized in that the sodium salt is converted to sodium hydroxide solution and acid by way of electrodialy-sis.
14. The process according to claim 13, characterized in that the regenerated acid is reused in the process.
15. The process according to any one of the claims 1 to 14, characterized in that if sodium sulfate is formed pre-cipitation is effected with calcium oxide and the resultant gypsum and/or the resultant sodium hydroxide solution are supplied to a recycling process or marketed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4227511.3 | 1992-08-20 | ||
| DE4227511A DE4227511C1 (en) | 1992-08-20 | 1992-08-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2141575A1 true CA2141575A1 (en) | 1994-03-03 |
Family
ID=6465925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2141575 Abandoned CA2141575A1 (en) | 1992-08-20 | 1993-08-16 | Process for disposing of sodium-sulphur accumulator cells |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0656154B1 (en) |
| JP (1) | JPH08500465A (en) |
| AT (1) | ATE134280T1 (en) |
| CA (1) | CA2141575A1 (en) |
| DE (2) | DE4227511C1 (en) |
| WO (1) | WO1994005054A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4419695C1 (en) * | 1994-06-04 | 1995-08-10 | Fraunhofer Ges Forschung | Active material dissolution from alkali metal battery fragments |
| JP2980844B2 (en) * | 1996-06-11 | 1999-11-22 | 東京電力株式会社 | Method for recovering Na from sodium-sulfur battery |
| DE19906879B4 (en) * | 1999-02-19 | 2014-03-27 | Datasec Electronic Gmbh | Electronic locking and monitoring system |
| EP2662329A1 (en) * | 2012-05-11 | 2013-11-13 | Creachem SA | Peroxygen release compositions and method for producing them |
| JP6476598B2 (en) * | 2014-06-03 | 2019-03-06 | 三菱マテリアル株式会社 | Method for recovering sodium from sodium-sulfur battery, apparatus for recovering sodium from sodium-sulfur battery |
| KR102134719B1 (en) * | 2018-11-07 | 2020-07-16 | 주식회사 티에스케이프리텍 | Recycling apparatus for wasted lithium ion battery and method for the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3927225A1 (en) * | 1989-08-18 | 1991-02-21 | Asea Brown Boveri | METHOD FOR DISPOSAL OF STORAGE CELLS |
| IT1237502B (en) * | 1989-10-26 | 1993-06-08 | Nuova Samin Spa | PROCEDURE FOR THE TREATMENT OF EXHAUSTED BATTERIES |
| DE3942516C1 (en) * | 1989-12-22 | 1991-08-01 | Degussa Ag, 6000 Frankfurt, De | |
| US5015541A (en) * | 1990-03-15 | 1991-05-14 | Eveready Battery Company, Inc. | Process for neutralizing sulfur-containing cells |
-
1992
- 1992-08-20 DE DE4227511A patent/DE4227511C1/de not_active Expired - Lifetime
-
1993
- 1993-08-16 EP EP19930919069 patent/EP0656154B1/en not_active Expired - Lifetime
- 1993-08-16 JP JP50589494A patent/JPH08500465A/en active Pending
- 1993-08-16 DE DE59301652T patent/DE59301652D1/en not_active Expired - Fee Related
- 1993-08-16 AT AT93919069T patent/ATE134280T1/en not_active IP Right Cessation
- 1993-08-16 CA CA 2141575 patent/CA2141575A1/en not_active Abandoned
- 1993-08-16 WO PCT/EP1993/002181 patent/WO1994005054A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| DE4227511C1 (en) | 1993-07-22 |
| DE59301652D1 (en) | 1996-03-28 |
| EP0656154B1 (en) | 1996-02-14 |
| ATE134280T1 (en) | 1996-02-15 |
| EP0656154A1 (en) | 1995-06-07 |
| WO1994005054A1 (en) | 1994-03-03 |
| JPH08500465A (en) | 1996-01-16 |
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