October 9, 2001

BENEFICIAL RECYCLING

OF METAL REFINING WASTES

VIA GASIFICATION

by

Dr. Steven C. Vick

and

Mr. Hans O. von Steiger

Gasification Technologies 2001

October 9, 2001

Gasification – A Process Technology

Incredibly flexible

Broadly applicable

Tremendously effective

Amazingly efficient

Highly economical

Environmentally superlative

The Best Thing Since Sliced Bread

October 9, 2001

Gasification – For the Conversion of

A Broad Range of Materials:

• Coal

• Petroleum Coke (high sulfur)

• Bio Mass Solids

• Municipal Solid Wastes

• Industrial Wastes

• Everything but the Kitchen Sink

• Well, OK, maybe even the Kitchen Sink

October 9, 2001

Gasification – To A Synthesis Gas with Utility for:

o Generating Electric Power and Steam

o Methanol

o Acetic Acid and Derivatives

o Hydrogen

o Ammonia

o Oxochemicals

o So many other uses, I couldn’t begin to tell you!

October 9, 2001

A process technology that is designed and operated for the purpose of producing synthesis gas (a commodity which can be used to produce fuels, chemicals, intermediate products, or power) through the chemical conversion of carbonaceous materials; and

GTC Definition of Gasification

October 9, 2001

A process that converts carbonaceous materials through a process involving partial oxidation of the feedstock in a reducing atmosphere in the presence of steam at temperatures sufficient to convert the feedstock to synthesis gas, to convert inorganic matter in the feedstock (when the feedstock is a solid or semi-solid) to a glassy solid material known as vitreous frit or slag, and to convert halogens into the corresponding acid halides; and

GTC Definition of Gasification

October 9, 2001

A process that incorporates a modern, high-temperature pressurized gasifier (which produces a raw synthesis gas) with auxiliary gas and water treatment systems to produce a refined product synthesis gas, which when combusted produces emissions in full compliance with the Clean Air Act.

GTC Definition of Gasification

October 9, 2001

Gasification --- Question of Dioxins and Furans

October 9, 2001

Electrolytic Cells for Aluminum Manufacture

October 9, 2001

Schematic – Typical Aluminum Electrolytic Cell

October 9, 2001

Analysis of Spent Aluminum Potliner

24.3Fixed Carbon95.3Solids

4.1Volatiles71.0Ash

0.6MoistureProximate Analysis

October 9, 2001

Analysis of Spent Aluminum Potliner

8.0Arsenic ppm146.0Cyanides ppm

16.7Fluorine0.3Sulfur0.6Nitrogen1.2Oxygen0.3Hydrogen

26.2CarbonUltimate Analysis

October 9, 2001

Analysis of Spent Aluminum Potliner

<0.1V2O 5

<0.1MnO2.6CaO<0.1Cr2O32.8Fe2O3

<0.1P2O50.8K2O0.4TiO226.6Na2O0.5SO339.9Al2O3

0.4MgO13.6SiO2

Ash Analysis

October 9, 2001

Selected Treatment Standards for SPL

1.4 mg/L26.1 mg/kgArsenic

1.2 mg/L590 mg/kgCyanide(total)

35 mg/LNAFluoride

WastewatersNon-WastewatersComponent

October 9, 2001

Spent Aluminum Potliner – As Received

October 9, 2001

SPL Particle Size Distribution After Milling

100.000.00.25100.001.110.250.1698.896.110.160.0992.788.670.090.07187.115.210.0710.05478.9015.890.0540.03663.0163.010.036

Distribution

Wt %Particle Size Class- mmfrom to

October 9, 2001

Spent Potliner Particle Size Distribution Function

October 9, 2001

Particle Size Distribution Comparison

October 9, 2001

Entrained Flow Gasifier with Cooling Screen

October 9, 2001

Gasifier Cooling Screen – Detail

October 9, 2001

Raw Synthesis Gas Analysis

215 BTU/scfCalorific Value<0.4 mg/m3Hydrogen Cyanide<1.0 mg/m3Fluoride compounds<268 mg/m3Carbonyl Sulfide<150 mg/m3Hydrogen Sulfide30.9Nitrogen19.4Carbon Dioxide 32.5Carbon Monoxide17.1HydrogenVolume PercentComponent

October 9, 2001

Analysis of Vitreous Frit from SPL

1.6Fixed Carbon0.4Volatiles

91.9Ash6.1Moisture

Proximate Analysis

October 9, 2001

11.0Arsenic ppm20.3Cyanides ppm14.4Fluorine

0.2Sulfur0.0Nitrogen0.0Oxygen0.2Hydrogen1.6Carbon

Ultimate Analysis

Analysis of Vitreous Frit from SPL

October 9, 2001

<0.1V2O 5

<0.1MnO4.6CaO<0.1Cr2O34.5Fe2O3

0.7P2O50.5K2O0.4TiO220.8Na2O0.2SO335.7Al2O3

0.6MgO19.0SiO2

Analysis of Vitreous Frit from SPL

October 9, 2001

100.0014.351.0085.658.311.000.6377.342.120.630.5075.2236.670.500.2538.5525.290.260.1613.2610.230.160.093.032.000.090.0561.031.030.056

Distribution

Wt %Particle Size Class- mmfrom to

Vitreous Frit Particle Size Distribution

October 9, 2001

Leaching Characteristics of Frit – Mod. TCLP

Final pH ---------- 7.97Cyanide ---------- 0.014 mg/L(total)Cyanide ---------- <0.005 mg/L(amenable)Fluoride ---------- 180 mg/LArsenic ---------- <0.005 mg/LOther metals------ < 0.01 mg/L

Sb, Ba, Be, Pb, Ca, Cr, Ni, Hg, Se, Ag, Tl*, V*,

October 9, 2001

pH Fluoridein mg/L

9.75 4307.97 1806.84 71

0

100

200

300

400

500

0 5 10 15

pH (final)

Fluo

ride

(mg/

L)

Relationship of Fluoride Leaching to pH

October 9, 2001

NASolidsNAFixed Carbon

6.16Volatiles65.36Ash

NAMoisture

Proximate Analysis

Analysis of Process Water Solids

October 9, 2001

14.0Arsenic ppm12.2Cyanides ppm15.7Fluorine

1.2SulfurNANitrogenNAOxygen0.4Hydrogen

28.48CarbonUltimate Analysis

Analysis of Process Water Solids

October 9, 2001

<0.1V2O 5

<0.1MnO2.5CaO

<0.1Cr2O33.2Fe2O3

<0.1P2O50.4K2O

0.3TiO219.0Na2O

0.2SO335.6Al2O3

0.4MgO19.0SiO2

Analysis of Process Water Solids

October 9, 2001

Metals Partitioning – Low Volatility Metals General Gasification

PWSPWFritMetal

5986V

41284Cr

4888Ni

5887Mn

<0.32971Cu

-1090Co

October 9, 2001

<0.552.047.5V

-33.266.8Cr

0.497.42.2Ni

<0.242.157.8Mn

-21.778.3Cu

---Co

PWSPWFritMetal

Metals Partitioning – Low Volatility Metals SPL Gasification

October 9, 2001

Metals Partitioning – Volatile Metals General Gasification

-6436Sn

<0.2928Zn

-100-Hg

<0.3964Cd

<0.2964Pb

46333As

PWSPWFritMetal

October 9, 2001

Metals Partitioning – Volatile Metals SPL Gasification

---Sn

<0.257.442.4Zn

---Hg

---Cd

0.0271.328.3Pb

0.860.538.0As

PWSPWFritMetal

October 9, 2001

Corrosion Testing

Testing of Corrosion Coupons

Showed No Unusual or Unacceptable

Corrosion Under the Test Conditions

October 9, 2001

CONCLUSIONS

•Spent Aluminum Potliner may be gasified

•Products are:

o Synthesis Gas

o Vitreous Frit

o Process Water Solids – may be recycled

•Contained carbon exhibits low reactivity

•100 % Beneficial Recycling believed achievable

October 9, 2001

Conclusions - Synthesis Gas

•Similar to that from other feeds

•Non-detectable levels of

o Fluoride

o Cyanides

o Arsenic

o Dioxins/Furans

o Other TCLP Constituents

October 9, 2001

Conclusions – Vitreous Frit

•Superb Leaching Characteristics

o Non-detectable Cyanides

o Non-detectable Arsenic

o Non-detectable TCLP Constituents

o Fluoride low (but high contained level)

•Better than Currently Available Technology

•Easily Achieves EPA Treatment Standards

October 9, 2001

Conclusion ---

SLAGGING GASIFICATION - - - - - - -

THE FIRST TECHNOLOGY

FOR THE 100 PERCENT

BENEFICIAL RECYCLE

OF SPENT ALUMINUM POTLINER

October 9, 2001

SLAGGING GASIFICATION

BEST DEMONSTRATED AVAILABLE TECHNOLOGY

BENEFICIAL RECYCLING

WASTE MATERIALS

Gasification Technologies 2001

October 9, 2001

BENEFICIAL RECYCLING

OF METAL REFINING WASTES

VIA GASIFICATION

by

Dr. Steven C. Vick

and

Mr. Hans O. von Steiger

Gasification Technologies 2001