part 2 marketing and waste collection survey (imnr...
TRANSCRIPT
Part 2
Marketing and Waste Collection Survey (IMNR Research Report 1)
IMNR INSTITUTE FOR NONFERROUS AND RARE METALS
CLASSIFIED
INSTITUTUE FOR NONFERROUS AND RARES METALS
- S.C. I. M. N. R. S.A. BUCURESTI –
RESEARCH REPORT
PILOT PROJECT NAMED:
” PROMOTION OF HEAVY METAL RECYCLING USING
EXISTING SMELTING FACILITY „
REPORT 1
- BUCHAREST - nov-dec. 2002
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IMNR INSTITUTE FOR NONFERROUS AND RARE METALS
GENERAL DIRECTOR
dr. eng. Teodor Velea
RESEARCH TEAM
dr. eng. T. Velea
dr. eng. A. Manea
eng. M. Gorinoiu
eng. D. Stoica
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CONTENT
CHAPTER I Target Smelters I. S.C. SOMETRA S.A. �4 II. R.B.G. PHOENIX S.A. �7 III. S.C. ROMPLUMB S.A. �10 CHAPTER II
Target Factorys, Which Generate Heavy Metal Wastes Through Manufacturing Process
1. S.C. PROGRESUL S.A. Ploiesti �12 2. S.C. BICAPA S.A. Tarnaveni �13 3. S.C. CELPI S.A. Bucuresti �14 4. S.C. IND. Sarmei S.A. Campia Turzii �15 5. S.C. Santierul Naval S.A. Braila �15 6. S.C. Santierul Naval S.A. Turnu Severin �16 7. S.C. ROMCAR S.A. Bucuresti �16 8. S.C. MEFIN S.A. Sinaia �17 9. S.C. MECORD S.A. Oradea �17 10. S.C. RADIATOARE S.A. Brasov �17 11. S.C. TEHNOFRIG S.A. Cluj �18 12. S.C. DUCTIL S.A. Buzau �18 13. S.C. Santiere Navale S.A. Constanta �19 14. S.C. Santiere Navale S.A. Mangalia �19 15. S.C. SIDEX S.A. Galati �20
CHAPTER III
Company Which Generate Heavy Metal Wastes Through Equipment Disintegration
16. S.C. ROMTELECOM S.A. �21
CHAPTER IV General Data for Pastes Used Battery
17. S.C. REMAT S.A. �23 CHAPTER V Prices of Main Wastes � 30 ANNEX I-VII Schematic-Flowsheet �31-36
ANNEX VIII Result of Identification of Target Waste (Table) �37
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CHAPTER I Target Smelters
In period 28.10 �30.11.2002 was investigated follow smelters: ! Sometra S.A. Copşa Mica, ! R.B.G. Phoenix S.A. Baia Mare ! Romplumb S.A. Baia Mare
Details are current condition of operation, waste disposal and recycling in the target smelters as follow:
I. Factory Name: S.C. SOMETRA S.A.
1.1. General
Location: Copsa Mica , Sibiu County street Fabriciilor 1; phone & fax +004 069 840 325 / 840 326; telex 66 236 SMTRA, ROMANIA
Content of business: Company goal: Pirometallurgycal processing of zinc concentrates and lead concentrates for non-ferrous metals extraction Principale activity:
• Lead , metallurgical zinc and refined zinc • Antimony, bismuth • d`Oré alloy
Preponderant activity: Pirometallurgycal processing of zinc and lead concentrate
Number of employee: 1350 (year 2002)
Balance sheet as at 31.12.2001: c.a. 20 000 000 $
Contact person: Leonidas KOUDOUMOGIANNAKIS TECHNICAL DIRECTOR
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IMNR INSTITUTE FOR NONFERROUS AND RARE METALS 1.2. Process Flow & Internal Wastes Management
Facility and process flow: I.S.P. MORGAN technology for pirometallurgycal processing of zinc/lead concentrates Schematic flowsheet � ANNEX I
Capacity: 145 0000 ton / year concentrates
Raw material: zinc concentrates lead concentrates complex concentrates
Production record: (year 2000) Pb: 27 185 ton / year Zn: 52 854 ton / year
Waste tratament & gas emission: • Gas dry cleaning for technollogical gases with SO2 and dust .
Dalamatic fillter. • Gas dry cleaning sistem (gas+dust) by I.S.P. • Factory chimney (250 m) • Plant for sewage treatment and dump slurry-SENAE
Type and amount of internal wastes: (present and historical generation)
2000 2001 2002 (8 mont) Type internal wastes
ton ton ton 1. Zn-Pb drosses 8 443 12 125 8 602
2. Blue Powder 10 708 11 343 7 066
3. Agglomerating Dust 9 537 10 261 12 367
5. Cu-Pb drosses 6 142 4 986 2 986
6. Slag 53 147 47 990 29 031
7. Sludge/dust-deposit 12 895 13 068 10 570
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Analysis:
Type waste (%)
Zn-Pb drosses
29.55%Zn; 40.99%Pb; 0.26%Cu; 3.01%Fe; 2.89%S; 9.2%H2O (0.026%Bi; 0.056%Sb; 0.1%Cd; 0.12%As ; 0.069%Sn ; 6.43 SiO2; 2.82%CaO)
Blue powder 21.46%Zn; 39.76%Pb; 0.39%Cu; 4.32%FeO; 11.45%S; 25%H2O
Agglomerating Dust 27.98%Zn; 17.56%Pb; 1.26%Cu; 8.08%Fe; 1.79%S; 3% H2O
Slag 6.5%Zn; 1.12%Pb; 0.6%Cu
Cu-Pb drosses 1.25%Zn; 46.23%Pb; 18.39%Cu; 2.02%Fe; 1.3%S (2.5%Sb; 0.1%Bi; 1.2%As)
Slurry S.E.N.A.E. 0.8%Zn; 2.2%Pb; 0.086%Cu Present method of waste treatment:
Type internal
wastes method
Zn-Pb dross Recirculation to charge for agglomeration, depositing
Blue Powder Recirculation to charge for agglomeration, depositing
Agglomerating Dust Recirculation to charge for agglomeration, depositing
Cu-Pb dross/ashe Depositing and market-sale
Slag Depositing and market-sale
Slurry/dust (SENAE)
Depositing (Recirculation to charge for agglomeration and market-sale)
1.3. External Wastes Treatment: - 1.4. Problems in Terms of Waste Management: -
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II. Factory Name: R.B.G. PHOENIX S.A.
2.1. General
Location: Baia Mare, jud. Maramureş, ROMANIA street Eliberării 15 phone +40 (0) 62 217 812 fax +40 (0) 62 217 813 E-mail: [email protected] Website: www.rbgphoenix.com
Content of business:
Company goal: Pirometallurgycal processing of copper concentrates and gold-bearing concentrates for non-ferrous metals extraction Principale activity:
• Metallurgycal industry • Production of preciouses metalls and others
non-ferrous metals (copper production) Preponderant activity: Pirometallurgycal processing of copper concentrates
Number of employee: 686 (year 2002) Balance sheet as at 31.12.2001: c.a. 30 000 000 $
Contact person: Florian Dumitru Medium Vice-president
2.2. Process Flow & Internal Wastes Management
Facility and process flow: OUTOKUMPU technology for pirometallurgycal processing of copper concentrates Schematic flowsheet � ANNEX II
Capacity: 160 000 ton / year concentrate
Raw material: copper concentrate pirytes (gold-bearing) concentrate
Production record: (year1999) 60 000 Cu ton
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Waste tratament & gas emission:
• Gas dry cleaning system (gas+dust) of dry (I+II) to prepare charge • Gas dry and humid cleaning for technollogical gases with SO2 and
dust . Sulphuric acid plant. • Gas dry cleaning sistem (gas+dust) of converter and thermal reffining • Factory chimney • Plant for sewage treatment and dump slurry-SENAE
Type and amount of internal wastes:
historical generation deposit 2000 2001 2002 Type internal wastes ton ton ton
1. solderings 38 51 30
2. dust (electric-filter) 425 512 375
3. Slurry 208 322 185
4. Slag 26 524 21 230 19 534
5. Dust converter 263 332 210
6. Slag converter - 380 -
7. Dust thermal refining 232 312 212
8. Slag thermal refining 652 821 554
9. Slurry (SENAE) - 421 -
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Analysis: Type waste (%)
Dust (electric-filter)
4.16%Zn; 4.5%Pb; 16.25%Cu; 27.5%Fe; 10.25%S; (2.5%As; 0.24%Cd )
Solderings (waste-heat boiler)
7.26%Zn ; 6.45%Pb ; 14.15%Cu ; 20.5%Fe; 8.25%S; (3.28%SiO2; 1.12%As; 0.28%Cd )
Slurry 2.45%Zn ; 28.92%Pb ; 5.32%Cu ; 13.17%Fe; 8.86%S; (4.58%SiO2; 0.24%As; 0.10%Sb )
Slag 2.42%Zn ; 0.42%Pb ; 1.18%Cu ; 1.56%Fe;
Dust converter 6.84%Zn ; 34.12%Pb ; 4.37%Cu ; 1.26%Fe;
Slag converter 2.57%Zn ; 1.16%Pb ; 7.25%Cu ; 1.02%Fe;
Dust thermal refining 7.25%Zn ; 26.3%Pb ; 4.25%Cu ; 11.26%Fe; (1.25%As; 0.02%Sb)
Slag thermal refining
1.63%Zn ; 1.27%Pb ; 39.42%Cu ; 17.60%Fe; 0.11%S; (4.47%SiO2; 0.005%As; 0.024%Sb )
Slurry S.E.N.A.E. 1.3%Zn ; 1.02%Pb ; 3.5%Cu ; 1.2%Fe; (1.5%As)
Present method of waste treatment: 1. solderings Recirculation to charge furnace 2. dust (electric-filter) Recirculation to charge furnace 3. Slurry Recirculation to charge furnace 4. Slag Recirculation to charge furnace, depositing/market-
sale 5. Dust converter Recirculation to charge furnace and depositing 6. Slag converter Recirculation to charge furnace, depositing/market-
sale 7. Dust thermal refining Recirculation to charge furnace and depositing 8. Slag thermal refining Recirculation to converter 9. Slurry (SENAE) Depositing (recirculation to charge furnace /market-
sale) 2.3. External Wastes Treatment: - 2.4. Problems in Terms of Waste Management: -
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III. Factory Name: S.C. ROMPLUMB S.A.
3.1. General
Location: Baia Mare, MARAMUREŞ Street: Gutinului, nr. 9 phone & fax: 21 05 40 / 21 01 10 ROMANIA
Content of business: Company goal: Pirometallurgycal processing of lead concentrates for lead metal extraction Principale activity: Plumb bullion Preponderant activity: Pirometallurgycal processing of lead concentrates
Number of employee: 740 (year 2002)
Balance sheet as at 31.12.2001: -
Contact person: Uta Vasile GENERAL DIRECTOR
3.2. Process Flow & Internal Wastes Management
Facility and process flow: Watter Jacket technollogy- pirometallurgycal processing for lead concentrates Schematic flowsheet � ANNEX III
Capacity:
28 000 ton / year concentrate
Raw material: lead concentrates
Production record: (year1998) (year2002)
Pb bullion: 7708 ton / year Pb bullion: 7700 ton / year
Waste tratament & gas emission:
• Gas dry cleaning of sintering • Gas dry cleaning of Watter Jacket smelting
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Type and amount of internal wastes: (present and historical generation)
2000 2001 2002 Type internal wastes ton ton ton
1. dust 2 636 2 244 2 358
2. slurry - 28.5 40
3. slag 24 591 32 180 32 282 Analysis:
Type waste (%)
Dust 8,8%Zn; 48,12%Pb; 0,1%Cu; 1,2%Fe (0.54%As; 2.3%Cd; 0,006%In)
Slurry 1.45%Zn ; 22.3%Pb ; 0,35%Cu ; 38-42%Fe; 28-335%SiO2
Slag 4.52%Zn ; 1-4%Pb ; 0.58%Cu ; 12.16%Fe;
Present method of waste treatment:
Wastes are recirculation in technollgycal flow 3.3. External Wastes Treatment: - 3.4. Problems in Terms of Waste Management: -
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IMNR INSTITUTE FOR NONFERROUS AND RARE METALS
CHAPTER II
Target Factorys, Which Generate Heavy Metal Wastes Through Manufacturing Process
Between 28.10-30.11.2002, 15 companies generating heavy metal wastes from side commercial activities have been investigated. These side activities were: production of white zinc, to metal cover (almost full thermal and electrochemical zinc covering - plate, strap, pipes, assembling pieces and steel profile), alloys, etc.
Details are current condition of operation, waste disposal and recycling in the target factory as follow:
A). Companies consuming metallic zinc R1 for white zinc (ZnO) manufacturing
None of the investigated companies is using any type of technology for
internal waste treatment. Wastes generated (ashes, dross and dross-conicle) resulting in this
factory condition are not properly collected and stored . 1). Factory Name: S.C. PROGRESUL S.A. Ploiesti, conty Prahova
a). Content of Business: Chemical Industry Plant for white zinc (ZnO) - manufacturing Zn R1 by SOMETRA Copsa Mica. For white zinc (ZnO) manufacturing for caoutchouc industry, utilise metallurgical zinc (Zn D) the same factory. b). Type and Amount of Generation/Deposit of the Wastes:
Type waste Generationton/year
Deposit ton
Zn dross 3 6 Zn ashe 1 3 Zn dross-conicle 1.5 4
c). Present Treatment: Deposited Without Treatment
d). Analysis:
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Type waste (%) Zn dross 74.3%Zn ; 1.72%Pb ; 0.27%Cu ; 0.5%Fe Zn ashe 77.8%Zn ; 6.27%Pb ; 1.52%Cu ; 1.52%Fe Zn dross-conicle 72.45%Zn; 12%Pb; 0.72Cu; 1.6%Fe
2). Factory Name: S.C. BICAPA S.A. Tarnaveni, conty Mures a).Content of Business: Chemical Industry, Plant for white zinc (ZnO) - manufacturing Zn R1 by SOMETRA Copsa Mica. For white zinc (ZnO) manufacturing for caoutchouc industry, utilise metallurgical zinc (Zn D) the same factory. b). Type and Amount of Generation/Deposit of The Wastes:
Type waste Generationton/year
Deposit ton
Zn dross 5 8 Zn ashe 3 5 Zn dross-conicle 4 7
c). Present Treatment: Deposited Without Treatment d). Analysis:
Type waste (%) Zn dross 77.4%Zn ; 1.85%Pb ; 0.53%Cu ; 0.85%Fe Zn ashe 77.9%Zn ; 8.12%Pb ; 1.82%Cu ; 1.22%Fe Zn dross-conicle 25.0%Zn; 2.26%Pb; 0.42Cu; 2.26%Fe
B).Companies consuming metallic zinc R1 for metallic coverings
In Romania, the most used metallic coverings are: ! Galvanization
The procedure consists of the deposition of protective metallic layers via electrolysis of the solutions of the corresponding salts. Almost all technical metals (excepting Al) can lead to galvanic coverings. The technique of the galvanic coverings is quite simple: the metallic items to be protected are immersed in a solution of their own salts, thus becoming the cathode. The protective metal is the anode. This procedure is used in the covering of Fe with Zn, Ni, Cr� ect. The widest used galvanic covering in Romania is the one with Zn
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! Thermal metallic covering The procedure consists of covering (e.g. Fe) with metals having the
melting point lower than the one of Fe (like Zn, Sn and Pb) The widest used metallic thermal covering is the one with Zn
The metallic coverings are not the main object of activity of the Romanian companies, thus they do not pay attention to collection, treatment, depositing and recycling of the wastes.
In Romania, ca. 95% of the companies performing galvanization (electrochemical covering) generate complex sludge because they collect the residual waters (washing waters, used electrolyte) from all production lines into a single collecting tank, where the neutralization takes place. An advantage of this method (if it may be called so) is that the widest used electrochemical covering is that with Ni. The treatment of the waste waters is done in two stages, with sodium hypochlorite.
The constant element in all samples was Fe - coming from the �interstage pickling� and washing stages which are done prior to the metallic covering stage (at galvanization, it is collected into the same single tank where the neutralization is performed).
The main elements differ from one company to another, function of its specific production needs.
All visited companies use Zn R1 from SOMETRA Schematic flowsheet � ANNEX IV÷VII
3). Factory Name: S.C. CELPI S.A. Bucuresti, conty Ilfov a). Content of Business: Energetic Industry It has a unit for thermal Zn covering and it is the only company (out
of all visited ones) which perform internal recycling of waste Zn dross via melting / distillation in a technical unit bought from Germany.
b). Single Waste Generate Is Zn Ase Resulting of Distillation Mufle
Type waste Generationton/year
Deposit ton
Zn ashe 3 5 c). Present Treatment: Depositing Without Treatment d). Analysis:
Type waste (%) Zn ashe 77.8%Zn ; 6.27%Pb ; 1.52%Cu ; 1.52%Fe
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4). Factory Name: S.C. IND. Sarmei S.A. Campia Turzii, conty Mures
a). Content of Business: Metallurgical Industry Plant for zinc thermal refining b). Type and Amount of Generation/Deposit of The Wastes:
Type waste Generation
ton/year Deposit
ton Zn dross 5 18 Zn ashe 3 12
c). Present Treatment: Depositing Without Treatment d). Analysis:
Type waste (%) Zn dross 88%Zn ; 7.2%Pb0.4%Cu ; 3.1%Fe Zn ashe 70.25%Zn ; 5.23%Pb ; 0.022%Cu ; 0.65%Fe
5). Factory Name: S.C. Santierul Naval S.A. Braila, conty Galati
a). Content of Business: Shipbuilding Yard Industry Plant for zinc thermal refining b). Type and Amount of Generation/Deposit of The Wastes:
Type waste Generation
ton/year Deposit
ton Zn dross 4 12 Zn ashe 2 15
c). Present Treatment: depositing without treatment d). Analysis:
Type waste (%) Zn dross 87.2%Zn ; 2.85%Pb0.08%Cu ; 3.8%Fe Zn ashe 80.25%Zn ; 5.23%Pb ; 0.06%Cu ; 0.68%Fe (0.056%Cd)
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6). Factory Name: S.C. Santierul Naval S.A. Turnu Severin conty Caras- Severin
a). Content of Business: Shipbuilding Yard Industry Plant for zinc thermal refining b). Type and Amount of Generation/Deposit of The Wastes:
Type waste Generationton/year
Deposit ton
Zn dross 2 10 Zn ashe 3 12
c). Present Treatment: d). Analysis:
Type waste (%)
Zn dross 89.2%Zn ; 2.15%Pb0.02%Cu ; 2.8%Fe Zn ashe 75.3%Zn ; 1.23%Pb ; 0.02%Cu ; 7.85%Fe (0.56%Al)
7). Factory Name: S.C. ROMCAR S.A. Bucuresti, conty Ilfov
a). Content of Business: Auto-Car Industry Electroplanting b). Type and Amount of Generation/Deposit of The Waste:
Type waste Generationton/year
Deposit ton
Zn sludge 2 5 c). Present Treatment: Depositing Without Treatment d). Analysis:
Type waste (%) Zn sludge 55%Zn ; 0.65%Pb ; 0.047%Cu ; 4.0%Fe; 48%H2O
(2.5%Cd) Proposal: to be used to the factory who prepare concentrates ores
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IMNR INSTITUTE FOR NONFERROUS AND RARE METALS
8). Factory Name: S.C. MEFIN S.A. Sinaia, conty Ploiesti
a). Content of Business: Fine Machinery Industry Electroplating b). Type and Amount of Generation/Deposit of The Waste:
Type waste Generationton/year
Deposit ton
sludge 1 3 c). Present Treatment: Depositing Without Treatment d). Analysis:
Type waste (%) sludge 11.7%Zn ; 0.82%Pb ; 0.69%Cu ; 21.0%Fe; 45%H2O;
(2.1%Cd) Proposal: to be used to the factory who prepare concentrates ores
9). Factory Name: S.C. MECORD S.A. Oradea, conty Bihor
a). Content of Business: Machinery Industry, Plant for electrochemical covering -galvanization b). Type and Amount of Generation/Deposit o fThe Waste:
Type waste Generation
ton/year Deposit
ton Zn sludge 5 8
c). Present Treatment: Depositing Without Treatment d). Analysis:
Type waste (%) Zn sludge 37.21%Zn ; 0.52%Pb ; 0.25%Cu ; 4.75%Fe; 46%H2O;
(1.2%Cd) Proposal: to be used to the factory who prepare concentrates ores
10). Factory Name: S.C. RADIATOARE S.A. Brasov, conty Brasov
a). Content of Business: Machinery Industry, Electroplanting
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b). Type and Amount of Generation/Deposit of The Waste:
Type waste Generationton/year
Deposit ton
sludge 8 2 c). Present Treatment: depositing without treatment d). Analysis:
Type waste (%) sludge 5.12%Zn; 0.7%Pb; 0.15Cu; 15.93%Fe (2.75%Cd;
3.5%Cr) 11). Factory Name: S.C. TEHNOFRIG S.A. Cluj, conty Cluj
a). Content of Business: Machinery Industry, Electroplanting b). Type and Amount of Generation/Deposit of The Waste:
Type waste Generationton/year
Deposit ton
sludge 5 1
c). Present Treatment: Depositing Without Treatment d). Analysis:
Type waste (%) sludge 1.39%Zn ; 2.03%Pb ; 0.45%Cu ; 2.43%Fe
(0,75%Cd; 0.37%Cr;) 12). Factory Name: S.C. DUCTIL S.A. Buzau, conty Buzau
a). Content of Business: Metallurgical Industry
Electroplanting b). Type and Amount of Generation/Deposit of The Waste:
Type waste Generationton/year
Deposit ton
sludge 2 5
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c). Present Treatment: Depositing Without Treatment d). Analysis:
Type waste (%) sludge 9.15%Zn; 0.46%Pb; 1.22Cu; 15.56%Fe; (1.5%Cd)
13). Factory Name: S.C. Santiere Navale S.A. Constanta, conty Constanta
a). Content of Business: Shipbuilding Yard Industry Electroplanting b). Type and Amount of Generation/Deposit of The Waste:
Type waste Generationton/year
Deposit ton
sludge 3 5 c). Present Treatment: Depositing Without Treatment d). Analysis:
Type waste (%) sludge 10.25%Zn; 0.26%Pb; 0.92Cu; 20.56%Fe (3.5%Cd)
14). Factory Name: S.C. Santiere Navale S.A. Mangalia, conty
Constanta
a). Content of Business: Shipbuilding Yard Industry Electroplanting b). Type and Amount of Generation/Deposit of The Waste:
Type waste Generation
ton/year Deposit
ton sludge 2 4
c). Present Treatment: Depositing Without Treatment d). Analysis:
Type waste (%) sludge 12.55%Zn ; 0.09%Pb ; 0.9%Cu ; 23.06%Fe (1.13%Cd)
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15). Factory Name: S.C. SIDEX S.A. Galati, conty Galati
a). Content of Business: Metallurgical Industry Plant for continouse thermal zinc covering, plant for non-ferrous alloy b). Type and Amount of Generation/Deposit of The Wastes:
Generation ton/year
Type waste
2002 estimed 2003 Zn dross 525 770 Zamac ashe 5 - Brass and bronze ashes 3 -
c). Present Treatment: Depositing Without Treatment d). Analysis:
Type waste (%) Zn dross 0.1-0.16%Pb ; 0.1-2%Al ; 0.1-0.5%Fe; Zn difference ;
( 10-15%ZnO from Zn) Zamac ashe 88,5%Zn ; 0.57%Pb ; 0.83%Cu ; 0,75%Fe (6,24%Al) Brass and bronze ashes 21%Zn ; 0.45%Pb ; 61,2%Cu ; 6,1%Fe (4,2%Al)
e).Price of Zn dross: 70÷85% from Zn LME
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CHAPTER III
Company Which Generate Heavy Metal Wastes Through Equipment Disintegration
16). Factory Name: S.C. ROMTELECOM S.A. a). Content of Business: Telecommunications b). Type and Amount of Generation/Deposit of The Wastes: ! Battery used - telecommunications
Type waste Generation (1
ton/year Deposit
ton Battery used: (telecommunications)
1-pastes - 165 2- lead plates+connectig lead bar - 7 (1 not in every year
Analysis :
Type waste (%) Pastes
-%Zn ; 71.25%Pb ; 0.01%Cu ; 0.15%Fe; 5.2%S; (0.3%Sb; 1.2%C)
lead plates+connectig lead bar 95%Pb ; 5% Sb
! Metalls cables - telecommunication
Copper cable contains the following main parts: o Copper wires: Consistis of circular copper conductor a purity of
99.97%, a density of 8. 8kg/dm3 and the nominal diameters in the range of 0.4-1.2 mm o Cable sheath:lead sheath or lead covered by polyethylene or PVC
shath o Others external layer: steel tapes covered by jute materials and
impregnated with bitumen, or steel tapes covered by polyethylene or PVC
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The following can be recovered from all these cables: o copper o lead o other materials, such as: steel scrap , plastic materials
Type waste Generation (1
ton/year Deposit
ton Cables used: (total) (telecommunications) - 5 000
1- Cu - 1 348 2- Pb - 2 486 (1 not in every year
used cables - telecommunication deposit
ROMTELECOM located in conty
Total cables (weight)
ton
Cu ton
Pb ton
Alba 258 59 96 Arges 100 22 57 Bacau 445 77 202 Mehedinti 296 86 209 Olt 270 71 174 Prahova 864 269 450 Brasov 263 65 145 Buzau 314 86 124 Hunedoara 539 167 263 Harghita 281 65 162 Constanta 150 18 51
c). Present Treatment: Depositing Without Treatment for Sale by
Auction
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CHAPTER IV
General Data for Pastes Used Battery
17). Company specific name: S.C. REMAT S.A.
a). Location: in every conty � under 42 companies b). Content of business: wastes colected and market-sale (ferrouse and
non-ferrouse) and colected and market battery used (lead and sulphuric acid) ! Battery used
Distribution of collected batery used in Romania, flowsheet � ANNEX
VIII c). Type and amount of generation/deposit of the wastes: In Romania, the consumption of battery (lead+acid sulphuric) per year
has an average over than 1 milion; from this quanttity, 60% are collected or exported.
It is appreciated that the polluted potential (per year) of the used battery uncontrolled deposited minimum is 10 000 tons for lead (4 500-5 000 tons for sulphuric acid)
Type waste Generationton/year
Depositton
Battery used1) 1. pastes 5 000 2. (grids and other) lead 8 000
100 000
1) source data: �ROMANIA LEAD ACID BATTERY RECYCLING PROGRAM� Prefeasibility Study, 1998)
d). Present treatment: depositing, not treatment-on sale at companies for recycling
e). Analysis (year 2002): Factory recycling battery used: Type waste (%)
NEFERAL S.A. 72.01%Pb ; 0.05%Cu ; 0.06%Fe; 6.9%S (0.5%Sb; 0.88%C)
PROMBAT S.A. 72.55%Pb ; 0.016%Cu ; 0.48%Fe; 5.01%S (0.046%Sb; 2.66%C)
Pastes factory source I.M.N.R. S.A. 72.3%Pb ; 0.08%Cu ; 0.1%Fe; 6.2%S
(0.2%Sb; 1%C) (Grids and other)lead 95%Pb ; 5% Sb
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IMNR INSTITUTE FOR NONFERROUS AND RARE METALS XRD analysis for paste shows the presence of the following species: anglesite, plattnerite , metallic lead (figure 1):
A - Anglesite PbSO4; P � Plattnerite β-PbO2; Pb � Metalic lead.
Figure 4.1 XRD Analysis for Pastes The chemical composition of the drained acid is presented in table 1.
Table 4.1 Chemical Composition of the Drained Acid (mg/l)
Drained
acid H2SO4
(g/l) Pb
(mg/l) Fe
(mg/l) Sb
(mg/l)As
(mg/l)Cd
(mg/l)Cu
(mg/l)Ni
(mg/l) Zn
(mg/l) Ca
(mg/l)
IMNR 150 2.2 32 3.7 1 1.08 4 0.56 10.1 25
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IMNR INSTITUTE FOR NONFERROUS AND RARE METALS
X1000, N+, reflected light,
imersion in cedar oil Agregates containing anglesite(white - blue, transparented),plattnerit and scrutiniyt (redbecause of the internal reflexesof the plattnerit), translucidecrystalls of anglesite
Mapboc
X250, N+, reflected light. Agregates containinganglesite (white - blue,transparented), plattnerit andscrutiniyt (red because of theinternal reflexes of theplattnerit)
X250, N+, reflected light, Agregates containing anglesite(white - blue, transparented), andplattnerit (red because of theinternal reflexes of the plattnerit)and lead metallic (blue -chagrinat aspect)
X1000, N+, reflected light, imersion in cedar oil
Agregates containing anglesite(white - blue, transparented) andplattnerit and (red because ofthe internal reflexes of theplattnerit)
Ag(wbeof me
2 - 25
X1000, N+, reflected light, imersion in cedar oil
ettalic lead, chagrinat aspect,gregates containing anglesitelattnerit and scrutiniyt (redecause of the internal reflexesf the plattnerit), transluciderystalls of anglesite
X1000, N+, reflected light, imersion in cedar oil
regates containing anglesitehite - blue) and plattnerit (redcause of the internal reflexes
the plattnerit) and leadtallic (blue - chagrinat aspect)
IMNR INSTITUTE FOR NONFERROUS AND RARE METALS
Figure 4.2 Structural Analyses of the Pastes from NEFERAL From the pastes smelting in short rotary furnace result as wastes volatile dusts and slags. The chemical compositions, XRD analysis and structural analysis of slags and volatile dusts are very different function of the processing recipes and the work mode (table 2, 3 and figure 3, 4, 5, 6).
Table 4.2 Chemical Compositions of the Slags (%) Slag source Pb Fe Sb Si Ca Mg Al S Cl Na C
NEFERAL 3.08 6.33 1.23 4.64 3.78 1.14 1.34 9.27 1.34 22.6 1.3
PROMBAT 17.54 15.89 0.26 3.5 1.1 0.36 0.8 10.06 2.2 8.74 4.41
IMNR 4.24 4.1 0.41 6.14 2.02 0.44 2.1 4.78 0.3 22 4.71
LEMATEC 69.54 6.77 3.54 0.68 0.2 0.22 0.18 4.08 1.2 0.13 0.94
ROMBAT 75.14 0.22 8.75 0.001 0.21 0.01 0.02 0.26 0.01 0.18 0.4
Table 4.3 Chemical Composition of the Volatile Dusts (%)
Volatile dust source Pb Fe Sb Si Ca Mg Al S Cl Na C
NEFERAL 57.23 0.04 1.96 0.028 0.08 0.015 0.023 6.42 3.2 4.03 1.5
PROMBAT 46.67 0.74 0.51 0.006 0.19 0.021 0.028 4.98 9.22 9.42 5.08
IMNR 47.93 1.76 0.69 0.04 0.075 0.4 0.03 5.14 6.04 6.28 9.84
XRD analysis for slag shows the presence of the following species (figure 3):
2 - 26
IMNR INSTITUTE FOR NONFERROUS AND RARE METALS
G- Galena PbS A - Anglesite PbSO4 Pb - Metallic lead Pb T- Thenardite Na2SO4 H- Halite NaCl MG - Maghemite/magnetite γFe2O3/ Fe3O4
Figure 4.3. XRD analysis for slags
Athtrmbeof
Agthetramabeofwh
Agthetramabeofof
X250, N+, reflected light, regates containing anglesite,nardite, halite (white-yellownspareted), magghemite,gnetite, metallic lead (red
cause of the internal reflexes magghemite or Pb oxides ),ite granules of PbS
Figure 4.4 Stru
X250, N+, reflected light, regates containing anglesite,nardite, halite (white-yellownspareted), magghemite,gnetite, metallic lead (red
cause of the internal reflexes magghemite), white granules PbS
of
ctural Analyses of the Slags
2 - 27
X1000, N+, reflected light, imersion in cedar oil
gregates containing anglesite,enardite, halite (white-yellowanspareted), magghemite,agnetite, metallic lead (redcause of the internal reflexes magghemite), white granules PbS
IMNR INSTITUTE FOR NONFERROUS AND RARE METALS Also, the slag sample contains weak crystallized material or amorphous which could not be identify. Because of the high atmospherically humidity, a part of material is leached and again crystallized during the measurements. By pastes smelting in reverberatory furnace result slags with high lead content (table 2). These slags are smelted again in rotary furnace. The untypical wastes are the slags coming from the processing of grids and other lead wastes from the plants which produce batteries. These slags have also high lead content (table 2) and are processed in rotary furnace. XRD analysis for volatile dusts is presented in figure 5.
The microscopic study shows that the volatile dust sample has micron and submicron dimensions, many times as aggregates. There were determined the same compounds determined by XRD and more lead as sulfur. The presence of lead sulfur and other compounds in quantities from 1 to 3% can be seen at microscope but can not be seen by XRD.
G - Galena PbS L- Laurionite Pb(OH)Cl C - Cotunnite PbCl2 H - Halite NaCl A - Anglesite PbSO4 Pb - Metallic lead Pb
Figure 4.5. XRD Analysis for Volatile Dusts
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IMNR INSTITUTE FOR NONFERROUS AND RARE METALS
Acoantrale
Agcoantraleaco
Agcoantraleaco
Acoantrleco
X250, N+, reflected light, regates containing laurionite,
tunnite, matlockite, haliteglesite (white - yellownspareted ), maybe metallicd, sulphures, oxides (a closedlour).
co
Aco-mcl
Figure 4.6 StructuNEFERAL,
X1000, N+, reflected light, imersion in cedar oil
gregates containing laurionite,tunnite, matlockite, haliteglesite (white - yellownspareted), maybe metallic
ad, sulphures, oxides (a closedlour).
Aco- mcl
g
yeo
ral Analyses of Volatile Dusts f I.M.N.R. and PROMBAT
2 - 29
X250, N+, reflected light, regates containing laurionite,
tunnite, thenardite, haliteglesite (white - yellownspareted ), maybe metallicd, sulphures, oxides (a closedlour).
X1000, N+, reflected light,
imersion in cedar oil gregates containing laurionite,tunnite, thenardite, haliteglesite (white - yellow
anspareted ), maybe metallicad, sulphures, oxides (a closedlour).
X250, N+, reflected light, regates containing laurionite,
tunnite, halite anglesite (whiteellow transpareted ), maybetallic lead, sulphures (ased colour).
X1000, N+, reflected light, imersion in cedar oil
gregates containing laurionite,tunnite, halite anglesite (whiteyellow transpareted ), maybeetallic lead, sulphures (aosed colour).
rom
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IMNR INSTITUTE FOR NONFERROUS AND RARE METALS
CHAPTER V
PRICES OF MAIN WASTES
1. WASTES CONTAINING ZINC
Price of zinc from wastes : (% Zn) from waste x (40-60%) from LME Zn 99,99
2. WASTES CONTAINING LEAD
- used battery: 60-85 USD/tone
- pastes from used battery:120-160 USD/ tone
- pipelines, wires: 75-85 % from LME Pb
3. WASTES CONTAINING COPPER - First quality: 95% from LME Cu
- Second quality. 85 % from LME Cu
- Third quality: 78-82 % from LME Cu
• Observations:
- Galvanizations sludge is less prices and we can got it for free
- Volatiles dusts form electrics fours in metallurgy plants can not be
separately catches, depending on zinc contents. In this moment
volatile dusts is recirculated or dump depositing.