part 2 marketing and waste collection survey (imnr...

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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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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mailto:[email protected]


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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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:


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


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:


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:


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:


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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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:


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;


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:


ton/year Deposit

ton Zn sludge 5 8


Type waste (%) Zn sludge 37.21%Zn ; 0.52%Pb ; 0.25%Cu ; 4.75%Fe; 46%H2O;


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:


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:


Deposit ton

sludge 5 1


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:


Deposit ton

sludge 2 5

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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:


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:


ton/year Deposit

ton sludge 2 4


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 -


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)


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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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

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ettalic lead, chagrinat aspect,gregates containing anglesitelattnerit and scrutiniyt (redecause of the internal reflexesf the plattnerit), transluciderystalls of anglesite


regates containing anglesitehite - blue) and plattnerit (redcause of the internal reflexes

the plattnerit) and leadtallic (blue - chagrinat aspect)


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


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


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

2 - 28


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,


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


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).


tunnite, halite anglesite (whiteellow transpareted ), maybetallic lead, sulphures (ased colour).


gregates containing laurionite,tunnite, halite anglesite (whiteyellow transpareted ), maybeetallic lead, sulphures (aosed colour).

rom

2 - 30


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.

part 2 marketing and waste collection survey (imnr...

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