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