EMERGING TECHNOLOGY REPORT:
RECLAMATION OF LEAD FROM SUPERFUND WASTE MATERIAL USING
                 SECONDARY LEAD SMELTERS
             RISK REDUCTION ENGINEERING LABORATORY
              OFFICE OF RESEARCH AND DEVELOPMENT
             U.S. ENVIRONMENTAL PROTECTION AGENCY
                    CINCINNATI, OHIO 45268

-------
                                          NOTICE


This material has been funded wholly or in part by the United States Environmental Protection Agency
under Contract CR-818199-01-0 to the Center for Hazardous Materials  Research.  It has been subject to
the Agency's review and it has been approved for publication as an EPA document. Mention of trade
names or commercial products does not  constitute endorsement or recommendation for  use.

-------
                                       FOREWORD


The Superfund Innovative Technology Evaluation (SITE) Program was authorized in the 1986 Superfund
Amendments. The program is a joint effort between EPA's Office of Research and Development and Office
of Solid Waste and Emergency Response. The purpose of the program is to assist the development of
hazardous waste treatment technologies necessary to implement new cleanup standards which require
greater reliance on permanent remedies. This is accomplished through technology demonstration designed
to provide engineering and cost data on selected technologies.

The  Risk Reduction Engineering Laboratory (RREL) is responsible fpr planning,  implementing and
managing research, development, and  demonstration programs to provide an authoritative,  defensible
engineenng basis for support of the policies, programs, and regulations of the EPA. This publication is one
of tne products of that research and provides a vital communication link between the research and the user
community.

This  project cpnsisted of demonstration of the use of secondary lead smelters to reclaim lead from a variety
of materials, including materials  found  at Superfund sites as well as other lead-containing wastes. The
demonstration consisted of feeding materials from five sources  - three Superfund sites, and two other
sources, to a secondary lead smelter to determine if the smelter could economically reclaim the lead.


                                                                      E. Timothy Oppelt, Director
                                                            Risk Reduction  Engineering Laboratory

-------
                                          ABSTRACT


There are over 3,000 sites across the United States contaminated wtth lead. Techniques to remediate
these sites include  standard stabilization/disposal technologies, reclamation of lead using secondary lead
smelters, soil  washing,  and biological  removal  technologies.

Through a Cooperative Agreement with  the U.S.  Environmental Protection Agency's Risk Reduction
Engineering Laboratory, the Center for Hazardous Materials Research CHMR), in  conjunction with a major
secondary lead smelter, has demonstrated that secondary lead smelters may be  used economically to
reclaim lead from a wide range of  lead-containing materials frequently found at Superfund  sites. Such
materials include battery case materials, lead dross,  and other debris containing between 3 and 70  percent


During  the  study,  CHMR and the smelter reclaimed  lead from  five sets  of materials,  including two
Superfund  sites  containing primarily battery cases, and one battery breaker/smelter site with a variety of
lead-containing  materials. Between 4 and 1600 tons of materials from each of these sites were excavated
and processed at the smelter, while the  research team assessed the effects on furnace operation and
performance. Two additional  sets of  materials, one from the demolition of a  house containing  lead-based
paint, and the other consisting of blasting  abrasive material from work on a  bridge coated wifn lead paint,
were also  processed in the smelter.  The results  showed that it was technically feasible to use the
secondary ead smelter to recjaim lead from  all of the materials. CHMR considered the use of materials
from a sixth site, which contained approximately 80% soil and 20% waste  battery cases. The site was
dropped from  consideration  for the study, because the smelter could not accept materials with such a high
soils concentration

CHMR  also assessed  the economics  of using  secondary lead smelters to  reclaim lead from  Superfund
sites, and developed a  method for estimating the cost of reclaiming  lead. This method develops cost as
a function of material excavation, transportation  and  processing costs combined with cost benefits received
by  the smelter (in the  form of recovered lead,  reduced fuel usage and/or reduced iron usage). The total
remediation costs using  secondary lead smelters for the sites and materials studied varied  between $35
and $374 per ton, based on January 1994 market prices  for lead.  The costs were primarily a function of
lead concentration, the market price for lead, distance from the smelter, and the amount of materials which
become incorporated into slag from  the  process, although other factors affected the economics as well.
Materials with high  concentrations of lead were significantly less expensive to remediate than those with
bw concentrations.  The cost to  remediate  materials  which left  few  slag residues in  the furnace was lower
than the cost to remediate materials which contained a significant amount of  material that remained in the
slag.

-------
                             TABLE OF CONTENTS

                                                                           Page

 NOTICE                                                                       ii
 FOREWORD                                                                    iii
 ABSTRACT                                                                    jv
 LIST OF TABLES  	    vii
 LIST OF FIGURES	    vii
 ACKNOWLEDGEMENTS  	    viii

1 . 0    INTRODUCTION	 1

       1.1     SOURCES OF LEAD CONTAMINATION	  1

             1.1.1   Lead Contaminated  Soils 	 2
             1.1.2   Battery Breaker Site Materials	 2
             1.1.3   Integrated Breaker/Smelter Site Materials  	 2
             1.1.4   Other Lead-Containing Materials  	   2

      1.2     AVAILABLE REMEDIATION  TECHNOLOGIES 	   2

             1.2.1   Solidification/Stabilization  	   3
             1.2.2   Capping 	   3
             1.2.3   Washing  	   3

 2.0     LEAD RECLAMATION USING SECONDARY LEAD SMELTERS 	 4

      2.1    TYPICAL SMELTING OPERATIONS	   4
      2.2     USE OF SECONDARY SMELTERS IN LEAD
              RECLAMATION FROM WASTE MATERIAL  	   4
      2.3     EVALUATION  METHODOLOGY, SITES, AND  MATERIALS  	   5

             2.3.1  Acquisition of Materials	    5
             2.3.2  Smelter Furnaces  	     9

      2.4     DATA AND SAMPLE COLLECTION	    10
      2.5    QUALITY ASSURANCE/QUALITY CONTROL	   10

3.0    RESULTS AND DISCUSSION 	  13

      3.1    PRODUCTION/PARAMETERS	    13

             3.1.1   Lead Production Ratio	    13
             3.1.2   Lead Loss Ratio  	    14
             3.1.3   Slag Disposal Ratio	  14

      3.2   FEED RATIOS OF SUPERFUND MATERIALS  TO TOTAL  FEED  	    14
      3.3   BENEFICIAL EFFECTS OF CERTAIN MATERIALS ON
              FURNACE PERFORMANCE	    15
      3.4   APPLICABILITY OF LEAD RECOVERY FROM
              WASTE MATERIALS	    16
      3.5   LEAD RECLAMATION EFFICIENCY	    17

4.0    LEAD RECLAMATION  ECONOMICS 	   19

      4.1     ON-SITE  EXCAVATION  	  19
      4.2    TRANSPORTATION  	  19

-------
 5.0

 6.0


 7.0
       4.3
       4.4
                        TABLE OF CONTENTS (continued)
       PROCESSING AT THE SMELTER
                                                      Page

                                                        19
             4.3.1
             4.3.2
             4.3.3
             4.3.4
            Additional Production Costs C
Base Cost CB	   20
	     '           	   20
                              	   20

                              	   20
                                  -PS.' ' '
            Additional  Disposal  Costs   Cdjsp
            Offsets for the Value of Lead and
              Reduction of Other Furnace Feeds.
             4.3.5   NET  Smelter  Processing  Cost  	  21
       OVERALL PROCESS ECONOMICS
CONCLUSIONS
RECOMMENDATIONS  FOR LEAD RECLAMATION
  AS A REMEDIAL APPROACH	
REFERENCES
                                                        22

                                                        23


                                                        24

                                                        25
APPENDIX A  RECLAMATION OF MATERIALS FROM BATTERY CASE PILES AT THE TONOLLI
             SUPERFUND SITE IN NESQUEHONING, PA

APPENDIX B   RECLAMATION  OF LEAD  FROM THE NL INDUSTRIES SUPERFUND SITE IN
             PEDRICKTOWN, PA

APPENDIX C   THE USE OF SECONDARY SMELTING TECHNOLOGY TO RECLAIM LEAD FROM
             IRON-SHOT BRIDGE BLASTING MATERIAL

APPENDIX D   THE USE OF SECONDARY LEAD SMELTERS TO RECLAIM LEAD FROM BATTERY
             CASE MATERIALS FROM THE HEBELKA SITE

APPENDIX E   THE USE OF SECONDARY LEAD SMELTERS TO RECLAIM LEAD FROM DEMOLITION
             MATERIALS FROM A HUD RENOVATION
                                      VI

-------
                              LIST OF TABLES

                                                                      Page

Table              Title

 1           SUMMARY OF THE EVALUATIONS.	 8
 2           INPUT, OUTPUT, AND OPERATING PARAMETERS 	   10
 3           METHODS USED TO MEASURE TEST PARAMETERS  	   11
 4           LEAD AND SLAG PRODUCTION COMPARISONS  	   13
 5           REQUIRED CHARACTERIZATION PARAMETERS	   17
 6           COST OF REMEDIATING SITES 	   22
 7           COMPARISON OF SMELTING AND OTHER TECHNOLOGIES 	   24
A-1          ANALYTICAL RESULTS FROM TEST MATERIALS	  A-2
A-2          SUMMARY OF EFFECTS ON BLAST FURNACE PERFORMANCE 	  A-6
A-3          BLAST SLAG ANALYTICAL RESULTS REGULAR FEED ONLY 	 A-10
B-1          DESCRIPTION OF FEED MATERIAL UPON ARRIVAL AT EXIDE  	  B-17
B-2          NL INDUSTRIES FEED MATERIALS ANALYSIS 	  B-18
B-3          REVERBERATORY LEAD FROM TEST MATERIAL VERSUS TYPICAL
             FEED LEAD FOR JANUARY 1992 PRELIMINARY INVESTIGATION	  B-19
B-4          ANOVA ANALYSIS OF BLAST SLAG PRODUCTION 	  B-20
C-1          PENNDOT BLASTING MATERIAL 	   C-2
C-2          TEST MATERIAL BLAST LEAD ANALYSIS 	   C-5
C-3          ANALYSIS OF SLAG SAMPLES 	   C-6
C-4          TEST BLAST FURNACE OPERATING  PARAMETERS 	  C-6
                             LIST OF FIGURES

Figure       Title

 1          SCHEMATIC OF SMELTING PROCESS 	  5
 2          SCHEMATIC OF RECLAMATION PROCESS.	  6
 3          PERCENT LEAD IN TEST MATERIAL VERSUS FEED RATIO 	  15
B-1          TEST FURNACE VS. CONTROL FURNACE SO2 EMISSIONS	  B-10
B-2          ANALYSIS OF AUGUST REVERBERATORY LEAD PRODUCTION 	  B-11
B-3          ANALYSIS OF AUGUST REVERBERATORY SLAG PRODUCTION 	  B-12
B-4          ANALYSIS OF SEPTEMBER REVERBERATORY LEAD PRODUCTION 	  B-13
B-5          ANALYSIS OF SEPTEMBER REVERBERATORY SLAG  PRODUCTION 	  B-14
B-6          ANALYSIS OF OCTOBER BLAST FURNACE LEAD PRODUCTION  	  B-15
B-7          ANALYSIS OF OCTOBER BLAST FURNACE SLAG PRODUCTION  	  B-16
                                    VII

-------
                                 ACKNOWLEDGEMENTS
The Center for Hazardous Materials Research  (CHMR) would like to acknowledge the cooperation received
throughout the project from  the U.S. Environmental  Protection Agency, Office of Research and
Development.   In particular,  we would  like to thank Ms. Laurel Staley, from the EPA's Superfund
Technology Demonstratbn Division who provided  helpful guidance on the project. The authors also
acknowledge the contributions  Mr.  Patrick Augustin in developing  and overseeing the early stages of the
project and Mr. Michael Royer, who provided many helpful comments to the original draft manuscript.
CHMR would  like to acknowledge the following  individuals from the research team who were responsible
for important contributions to this  project.

        Center For Hazardous Mater/a/s Research

        Mr. Stephen W. Paff                 Project Manager
        Mr. Brian Bosibvich                  Project Engineer
        Mr. Mark Ulintz                      Environmental  Specialist

        Exide Corporation

        Mr. Howard Master                  Plant Manager
        Mr. Steven Timm                    Engineer
        Mr. John  Baranski                   Vice  President, Environmental  Health and Safety

Work on this project was funded through Cooperative  Agreement Number CR-818199-01  established
between  the  U.S. Environmental  Protection Agency, Office of Research  & Development,  and  the Center
for Hazardous Material Research. The  organizations which contributed to  funding under this cooperative
agreement include the EPA, Exide Corporation, and CHMR. The members  of the project research team
appreciate the opportunity to  participate in this important project to research and develop a new and
innovative technology for the remediatbn and treatment of contaminated sites.  Inquiries  concerning this
report or the project may be addressed to:

        Mr. Stephen W. Paff, CHMM
        Manager,  Technology Development
        Center for Hazardous Materials Research
        320 William Pitt Way
        Pittsburgh, PA 15238
        (412)  826-5320
                                              VIM

-------
                                    1.0 INTRODUCTION

Lead is used in the production of various consumer and commercial items, from automobile and equipment
batteries to paints to crystal. This widespread use has made it one of the most common  contaminants at
sites on the National Priorities List (NPL). The most common current treatment of lead contaminated
wastes at Superfund sites is immobilization, either on-site or in a landfill. Remedial approaches which
involve recovery of lead are preferred over immobilization, which wastes the lead. One such remedial
approach is the use  of secondary lead smelters for recovery.
The initial  sections of this  report provide a brief overview of the sources and types of lead  contamination
and available remediation technologies. The remaining sections present results from a study of secondary
lead smelting as  a reclamation technology for lead-containing  waste material at Superfund sites.  The
economics of reclamation are examined to determine if the technology is economically competitive with
other  technologies.  Finally, a prognosis is  given for the use of secondary lead smelters for lead recovery.
1.1       SOURCES OF  LEAD CONTAMINATION
The prevalent use of lead in paints, gasoline additives,  and other products resulted  in wide dispersion
throughout the environment. A review of the literature [1-11] reveals the following sources of lead in the
environment:
            •   Lead acid battery  breaking activities;
            •   Primary and secondary lead smelting and refining;
            •  Production of lead  acid batteries;
            •   Production, storage and distribution of gasoline with leaded  additives;
               Solder use and manufacture;
            •   Plumbing;
            •   Ceramics  and  crystal manufacture:
            •  Paints (houses, bridges, ships), and  paint abrasive blasting material;
            •   Wire  manufacture  and coating;
            •   Automobile demolition (auto fluff);
            •   Construction  demolition (typically in plumbing and paints);
            •   Production and use of fishing sinkers;
            •   Pesticide  production and  use;
            •   Cathode-ray tube  production and  use;
            •   Rifle ranges and  munitions dumps, including state game land and military ranges;
               Ammunition  and  explosive manufacturing;
                Sewage sludge;
               By-products from metal production (e.g.,  electric arc furnace dust from steel  production);

-------
            •  Radioactive  shielding  (from x-ray machines to reactors); and,

            •  Other metals mining,  smelting,  and alloying (copper,  zinc, cadmium, and chromium).

These uses and sources of lead have contributed to many types of lead contamination, including lead
contaminated soils, battery breaker sites, and integrated breaker/smelter sites. These are discussed below.

1.1.1  Lead Contaminated Soils

Lead  in soils can be from a variety of  sources. The range of lead contamination from 436 Superfund sites
surveyed is between 0.16 and 366,000 mg/kg,  compared to up to 200 ppm in typical  uncontaminated  soils
[12,13] and 51,000 mg/kg in lead ores  used  at a major primary lead smelter [ 1 ].  Lead has been detected
in  soils in urban environments at concentrations  of up to 15,000 mg/kg due to a combination of automobile
exhaust, lead  paints  and batteries [15]. Lead  is commonly  found in soils at battery breaker sites in
concentrations  up to  100,000 ng/kg [8] and at gun clubs, with concentrations  up to  10,000 mg/kg [9].

Small amounts of lead are naturally present in the form of galena (PbS) although  upon  exposure to air it
is  converted to carbonates, sulfates, oxides and sulfur salts. Antnropomorpic lead sources in soils
typically  include acetates, organometallic compounds,  oxides,  elemental  lead,  sulfates,  halides,  sulfides,
and silicates [16].

The  United States Environmental  Protection  Agency (EPA) has  set acceptable lead levels in  soils at a
range of between 500 and 1,000 mg/kg. Otherlimits may be used based primarily on the likely uptake  of
lead in children or the proximity of the site to  residential areas [17].

1.1.2     Battery Breaker Site  Materials

The components of lead-acid batteries  include  the battery case,  lead electrodes  (typically screens), spacers
that separate the electrodes and prevent shorting, sulfuric acid, and lead battery paste (PbS04). In the
past,  the lead in lead-acid batteries was commonly removed  by cracking or breaking the battery shell,
draining the sulfuric acid into surface impoundments or lagoons, and pulling out as much of the metallic
and paste  lead as possible.

The  battery cases, spacers,  and some of the paste were sometimes  improperly disposed  or piled. Battery
cases  were often  disposed in drainage ditches and pits, and then buried  with soil. Sometimes the cases
were  burned in pits on site to recover additional lead.  These  materials, when segregated from the soil,
have  lead  concentrations ranging from 5,000  to  200,000 mg/kg [81.  Battery cases historically were made
from ebonite rubber, which is a hard, black rubber containing coke and coal dusts.   In  the late  1970's,
battery  manufacturers switched  to polypropylene cases, which  are readily  recycled.

Among the  materials typically found at battery breaker sites are  [1,4,19]:  broken  or whole battery cases,
jead  scrap, battery paste, sulfuric acid, lead debris and, (if the battery parts  were burned) partially
incinerated battery parts. There were approximately 20 battery breaker sites on  the NPL in 1991 [4].

1.1.3    Integrated Breaker/Smelter Site Materials

Some battery  breaking plants also reclaimed  lead on-site at  smelting facilities.  These facilities would sell
the recycled lead to  battery  manufacturers  for use in the production of new lead-acid  batteries. Materials
found at these sites include the same materials found at battery breaker sites,  as well as alloys, slag,
emissions  control dusts, dross,  lead oxides, and calcium sulfate  sludge from emissions  scrubbers.

1.1.4    Other Lead-Containing Materials

Other lead containing materials frequently  found at Superfund sites include  lead munitions and shot,
automobile  fluff, and  lead additive  residues.  Lead is very common, and  its forms vary greatly:  one site,
for example, contains over 10 million kg of lead-containing plastic wire  insulation, and a second  site
contains 20 million  kg of broken  lead-containing crystal, accumulated over several decades.

1.2     AVAILABLE REMEDIATION  TECHNOLOGIES

There are several options for  treating lead  contaminated sites, including soil  washing  or extraction,
immobilization, and reclamation. There are many variations of each type of remediation technology. A

-------
 survey  of records of decision (RODs) [18] indicated that over 70 percent of lead-contaminated sites were
 treated  with some type of immobilization  technology,  usually stabilization or disposal in a landfill  permitted
 to receive  hazardous waste. Less than 10 percent were treated using washing (size separation or
 extraction) technologies,  and less than 10 percent were treated using a reclamation process to recover
 usable  lead. The remainder were treated using  thermal technologies such as  incineration because the
 material was contaminated with organic  as well  as  heavy metal contamination.  Incineration destroys  the
 organic material,  but there is  typically lead-contaminated ash remaining  after treatment. This ash  usually
 retains the metals and therefore may also be hazardous  and require separate treatment and  disposal.
 Several  current treatment technologies are described below.

1.2.1   Solidification/Stabilization

 Solidification/stabilization technologies reduce the leachability of contaminants in the  soil. Stabilization
 refers to mixing of waste with reagents such as flyash to produce an end product that has about the same
 consistency as the original waste,  but with significantly reduced  contaminant  leachability. Solidification
 involves mixing the waste with ingredients,  such  as  binders or concrete, in cement mixers, pug mills, or
 other types of  equipment  to produce solid blocks  of material with considerable strength.  The mam goal is
 to lock the contaminants into  the material so they  do not leach out [1,4,21]. The two  technologies  are often
 used together [20,21].

 1.2.2   Capping

 Capping a waste site reduces the mobilization of the lead  by containing it on the site.  This prevents direct
 contact of the  cpntaminated  material with the  public and the surroundings. Capping is  attractive for  lead-
 contaminated soils, since  the lead is often relatively immobile in some  soil  systems [3].  Capping may be
 performed  with compacted clay, synthetic liners  or both.

 1.2.3   Washing

 Washing usually involves slurrying the waste with an aqueous solution, and then physically or chemically
 removing the  contaminants  using  acid, chelating agents, size separation, or solvents. Some soil washers
 separate the heavy metals based on the principle that most contaminants are concentrated in the finer soil
 fractions. These  technologies remove the finer soils  (which must be treated or  disposed)  and return the
 coarse material to the  site as clean soil [27].
 Although washing is generally used for soils, some companies are developing technologies to re
 wash the battery case  material. These systems use gravity separation or other techniques  to
                                                                                       remove and
                                                                                         segregate
the battery case's from soil,  rocks, or other debris, and scrubbers are used to thoroughly wash  the cases.
The clean battery cases can then be landfilled as non-hazardous waste [23,28]. It is difficult to  remove all
the lead  from ebonite battery cases, because the lead permeates the  slightly  porous  ebonite.
 Most soils washing technologies produce  either a soils fraction with high  lead concentration  or an hydroxide
 sludge, which must be disposed. However, several recently developed technologies  purport to remove lead
 from contaminated soils and produce metallic lead as a product [35], eliminating the need to dispose of
 residuals.
 Solidification/stabilization capping, and washing have been proven to be effective in remediating heavy
 metals in soils [4,19]. The use of these technologies,  however, has not been as successful when there  is
 large  debris, such as battery cases  or metallic lead, in the waste stream. Reclamation using  secondary
 lead smelters provides a more feasible  alternative for such materials.

-------
         2.0  LEAD  RECLAMATION  USING  SECONDARY  LEAD SMELTERS


Secondary lead smelters typically reclaim  lead from spent lead-acid  batteries. The use of secondary  lead
smelters to reclaim  lead from Superfund  or other waste feeds  involves slight rnodifiitions to the  normal
smetting process. This section provides a  description of typical secondary  lead smelting  processes, as  well
as the modifications required to process  the waste  material.

2.1      TYPICAL SMELTING OPERATIONS

The  evaluation was  conducted at  Exide/General Battery  Corporation's secondary lead smelter  location in
Reading, Pennsylvania. A  schematic of the process is shown  in  Figure 1. The operations at this  smelter
are typical of those found in the secondary lead smelting industry. As  part of normal  secondary  lead
smelting operations using reverberatory and blast furnace combinations, spent batteries received at  Exi de's
Reading smelter are crushed to release the sulfuric acid. Next they are  processed through a sink/float
system to separate the battery  cases from the heavier lead  particles.  The plastic  battery cases are
recycled on-site for  use in the production of new battery cases.

Reverberatory  furnaces are charged with  lead from the  sink/float system as well as other lead containing
material, and  are fueled with natural gas and oxygen. These furnaces  are tapped for slag, which typically
contains 60 to 70 percent  lead, and a pure (soft)  lead product.

Blast furnaces are  charged with the slag generated from the reverberatory  furnaces as well as other
lead-containing materials, and are fueled by coke and air enriched with oxygen. Iron and  limestone are
added as fluxing agents to enhance the lead  production  in the furnace by preventing  much of the lead from
remaining  in the blast furnace slag. Typical feed concentrations for  coke,  iron, and limestone are 5.7, 8,
and  0.9 weight percent,  respectively [29]. The blast furnaces are tapped continuously to remove lead and
intermittently to remove  the slag.   The blast slag, which contains primarily silica, iron oxides,  and some
lead,  is usually not  hazardous and is transported  to an off-site residual waste  landfill for disposal.

Lead produced in the blast and  reverberatory furnaces is transferred to the refining process where
additional metals are added to make specific lead alloys. The  lead is  then sent to the casting operations
where it is molded into ingots ("pigs") for use in the  manufacture of new lead-acid batteries. Waste
materials from Superfund  and  other sites are fed  either to the blast or reverberatory furnaces, depending
on the material type,  particle size, density, and other parameters.  The modifications  made  to enable
processing of this waste material are discussed in the following section.

2.2     USE OF SECONDARY SMELTERS  IN LEAD  RECLAMATION
        FROM WASTE MATERIAL

Prior work involving the use of secondary lead smelters to reclaim lead  focussed  on battery cases.  In
general, waste material was simply put through a smelter to  dispose of it. There were no quantitative
attempts made to analyze  the affects on  the furnace, or if the  reclamation itself was successful  [29].  One
goal of this research was to determine how the smelter furnaces react to the addition of various waste
materials.

The first step in the reclamation process, shown schematically in  Figure 2,  acquiring and transporting
the material to a secondary lead smelter. Generally, this involves excavation or collection,  pre-processing,
and transport to the  smelter. The lead-containing waste material is typically excavated from lead-add
battery Superfund sites or  collected from  other  sources, such as bridge  blasting or  demolition  operations.

Next, the material may require processing prior to entering the  furnace. Preprocessing includes screening
to remove soil, large  stones, or noncontaminated debris.  Materials larger than 12  inches cannot be fed
into the reverberatory  furnaces. These larger materials may cause jams in the belt  system that feeds the
reverberatory furnace,  or they may remain unburnt in the furnace for too long  a period of time. The   soil
and debris removed during pre-processing may be treated using one of the technologies described in
section 1.2,  since soil cannot be processed through a secondary smelter.

-------
    EXCAVATION OR

     COLLECTION
                                                        TRANSPORT OF MATERIAL
                          PRE PROCESSING
                              POCKS, SOILS, DEBRIS
                                          REVERB

                                         FURNACE
   LEAD TO
BATTERY PLANT
                                                              MIXING WITH

                                                          'TYPICAL SMELTER FEED
     SLAG TO DISPOSAL
                                        FIGURE 1
                             SCHEMATIC OF SMELTING  PROCESS
The pre-processed material is mixed with regular furnace feed from the crushing and sink/float system.
The feed rate is determined by lead content, size of the material, fuel values, and other parameters.

2.3     EVALUATION  METHODOLOGY,  SITES,  AND MATERIALS

The basic methodology during the project was to acquire quantities of the materials to be tested,
characterize these materials, process them through the secondary smelter, and observe their effects on
the furnaces through sampling and data  collection. The primary objective of the tests was to determine
how much and what types of materials could be fed to the furnaces without causing shutdowns or otherwise
adversely affecting smelter furnace performance.

2.3.1    Acquisition  of  Materials

Materials from three Superfund sites as well as  two additional sets of lead-containing materials were
processed during this project. The following sections provide a short description of each of the fiie
evaluations. The feed rates are presented as weight ratios of test material to total furnace feed. Table 1
presents a summary of the materials tested and the evaluations. More information on three of the sites
(Tonolli, NL Industries, and PennDOT)  can be found in appendices A, B, and C, respectively.

Tonolli  Superfund Site

The Tonolli site is a 30 acre battery breaking and smelting facility located in Nesquehoning, PA.  Piles of
ebonite rubber and polypropylene battery case  pieces were tested, without any pre-processing. The
material had an average lead  concentration of 3.5 percent. Approximately 84 tons of material were fed at
a ration of 10 percent through a reverberatory and blast furnace. The material was too large to be readily
processed In the reverberatory furnace,  but was successfully processed in the blast.

-------
       SPENT BATTERIES
             I	
                          PRETREATMENT
            EXPERIMENTAL
             WASTE FEED
      NATURAL GAS,
         OXYGEN —
      SOFT LEAD PRODUCT
                                  PLASTIC TO RECYCLE
                                  INTO NEW BATTERY
                                       CASES
                                  LEAD CONTAINING MATERIAL
                                              FURNACE GASES
                                          1
      REVER6ERATGRY
          FURNACE
           > 2000°F
              EXPERIMENTAL,
               WASTE FEED
       COKE, IRON
       AIR, OXYGEN
                SLAG (APPRGX, 70% Pb)

                            FURNACE GASES
             BUST
           FURNACE
             2200°F
           REFINING
           CASTING
               f
              OTHER
            LEAD FEEDS
     HARD LEAD
      PRODUCT
                            SLAG TO
      RCRA DISPOSAL
      LEAD TO BATTERY PLANT
     MONITORED
     EMISSIONS
SCRUBBER
BAGHOUSE
                                                       AFTERBURNER
                 DEWATERED SLUDGE     DUST TO FURNACE
                   fTO LANDFILL)      (FOR Pb RECLAMATION]
                                FIGURE 2
                    SCHEMATIC OF RECLAMATION PROCESS
Hebelka Superfund Site

The Hebelka site was a former autompbile junk and salvage yard located in Weisenburg Township, PA.
The site contained battey case debris mixed with soil that had an average lead concentration of 14.7
percent. Approximately 20 cubic yards of material were transported to the smelter. This material was first

-------
percent. Approximately 20  cubic yards of material were transported to the smelter. This material was first
reduced in size to less than 1/4-inch with  a hammermill. The material was successfully fed to the
reverberatory furnace at a feed ratio of 17 percent.

Demolition  Waste

Demolition waste  was  obtained  from a Housing and Urban Development  (HUD)  project. The waste
consisted of demolition debris mainly wood)  coated with lead based paint and had a lead  composition of
between 0.5 and 1 percent. The  test  material was shredded in a pallet shredder before It was smelted
The demolition debris was processed through both reverberatory furnaces at feed ratio of 10 percent test
material, by weight.  At this weight ratio the test  material comprised 50 percent of the  volume  fed to the
furnace. This  high volumetric ratio caused malfunctions in the  furnaces, so  the feed ratio was reduced to
5 percent, at which  point the material  was successfully fed.

NL Industries Superfund Site

The NL Industries site in Pedricktown, NJ, was an  integrated battery breaking, smelting, and  refining facility
with  its own on-site landfill.  There were a wide variety of materials at the site including lead slag, dross,
debris,  ingots, hard heads  (large chunks of metallic lead),  battery case  debris,  baghouse bags, and
contaminated pallets and iron cans. The evaluation was conducted in two parts: a preliminary investigation
and a full-scale investigation.

-------
                                               Table 1 Summary of the  Evaluations
Site
Tonolli
Hebelka
Laurel House
NL Industries
PennDOT
Site Description
Integrated battery
breaker
Auto junk & salvage
yard
Residence
Integrated battery
breaker & smelter
Bridge repainting
site
Site Size
30 acres
20 acres
N/A
11 acres
N/A
Test
Duration
5 days
1 day
1 day
3 months
1 day
Type of Mat' 1
Rubber & plastic
battery cases
Mainly plastic
battery cases
(some rubber)
Wood demolition
debris
lead slag, debris,
dross, ingots,
cases, baghouse
dusts
Iron shot bridge
abrasive
Amt.
Processed
84 tons
12 tons
4 tons
1570 tons
6 tons
Avg. Lead
Cone.
3.5%
14.7%
1%
30 to 60%
3.2%
Feed wt.
Ratio
20%
17%
5%
20 to 50%
13%
09

-------
During the preliminary investigation,  approximately 370 tons of all types of the above materials were
processed. Analyses revealed an average lead  concentration of 57  percent.  The  larger pieces of debris
were  removed and processed through a blast  furnace, while the bulk of the material was fed into a
reverberatory furnace at feed ratios of up  to 100 percent. The feed was sufficiently  dense to cause
breakdowns in the reverberatory furnace conveyor feed system, so the feed ratio was reduced to 50
percent test material,  by  weight.

During the full scale operation, approximately 1200 tons of material were transported to the smelter over
a three  month period.  For the first two  months, the test material, which contained approximately 50 percent
by weight lead, was processed  in the  reverberatory furnace, with a feed ratio of 20 to 30 percent. The ratio
was limited due to high amounts of calcium in the NL material. The high  calcium concentration slowed the
operation  of the furnaces.

The test material for the last month of the investigation consisted  mainly of larger pieces of slag and debris
with an average lead concentration of 30 percent.  This material was charged  directly to one of the blast
furnaces,  at a feed ratio  of  approximately  30 percent.

Pennsylvania Department of Transportation

The Pennsylvania  Department of Transportation PennDOT) used an iron-shot abrasive  blasting material
to remove old lead-based paint from  a  bridge in Belle Vernon, PA.  Sixteen 55 gallon steel drums of this
material, containing an average  of 3.2 percent lead, were processed at the smelter.

The bridge blasting  material was primarily iron (60 percent) with  5  percent calcium and 5 to 10  percent
moisture  content. The material contained too much  moisture to be incorporated  into the reverberatory feed.
The test material, including the  drum, was fed to one of the  blast furnaces at a feed ratio of approximatety
13 percent, by weight.

Bypass 601 Site Material

Material was obtained from the Bypass 601 Superfund site in Concord,  NC. The material consisted of
battery cases, mixed with soil.  Overall,  it contained approximately 1  percent lead. The material contained
approximately  80 percent soil and 20 percent battery cases. Based on this, the use of the reclamation
technology was deemed not to be feasible, unless a suitable  separation method  for the cases and soil was
developed. Although relatively simple size  separation methods for separating the soil from the battery
cases exist, they did not  appear likely to be economically viable, because the  soil contained significant
rocks and other debris which would remain with the battery cases, and because  a majority of the lead
would stay in  the soil. Therefore, the  site was dropped from consideration by this  study.

2.3.2  Smelter  Furnaces

Exide's secondary smelter has  two reverberatory furnaces and two blast furnaces. Each  reverberatory/blast
combination Is similar in  design and construction, as well  as production  potential. During the evaluation,
one furnace (either the reverberatory or blast, depending on the waste material) was charged with regular
smelter feed and the other was  charged with  regular feed mixed with  certain amounts of the waste  material.
This provided  "control" and  "test" furnaces,  and  comparisons could  be made between the two. Because
the furnaces normally undergo  wide fluctuations  in  production, the  comparisons were only valid when  the
furnaces were fed materials over four to six shifts.

Reverberatory furnaces are  often used to  remove metallic lead, and to  produce a fused  slag feed for the
blast  furnaces. The reverberatory furnace  has a two to three  hour residence time. The most  serious
problem encountered by introducing new feeds into the  reverberatory furnaces was the stacking of  unburnt
material  inside the furnace. This can  cause impaired performance or even damage to  the furnace. This
condition takes from one  to  several  hours  to occur,  so the furnaces  were still monitored after the test feed
was  stopped.

Blast  furnaces are used  to  reduce lead oxides to metallic  lead,  and remove them as product. The blast
furnace has a residence  time of several hours. Therefore the monitoring  of the  blast furnace charged with
test material was continued for several hours after the waste feed  is  discontinued. This allowed time to
more accurately determine if the test  feed had any  positive or negative affects  on the blast furnace
performance.

-------
2.4     DATA AND SAMPLE COLLECTION

Project personnel  collected samples and data to assess  the furnace  performance, characterize the input
material,  and characterize the furnace  outputs.  Table 2  shows the parameters that  were measured and
how  they were obtained. The input material parameters were characterized  to provide information related
to the feed, so that comparisons of the  effects of different feeds could be made. The furnace performance
parameters, such as air flow, oxygen usage, fuel usage,  and furnace feed rates provided  measurements
of the furnace performance while the experiments  were conducted, principally indicating  when  production
levels were falling or materials were clogging  in the furnace.  The output parameters were the most
important ultimate measurements of furnace performance - including  both production  rates and quality, as
well  as  residuals generation.

The  data generated from measurements and sample analyses were used to compare the performances
of the test and control furnaces. The amount  of lead  in each product is useful in  making a  mass balance
for the lead. The other parameters, such as  oxygen, air, and fuel, are useful in  determining the cost for
processing  the test material.

The  procedures for obtaining the samples  (marked  "S")  in Table 2 varied depending on the materials to
be  sampled.   For samples of incoming  waste  materials, representative  samples were obtained  by
compositing two to four individual grab  samples  obtained  from various locations and depths within the pile.
Generally,  a total of one to two Kilograms of such  materials were obtained. Duplicate samples were
obtained for approximately  25% of the samples.  Samples  of lead and slag produced in the furnaces were
obtained through the  use  of a small crucible placed into  the lead or slag  stream.


                                            TABLE 2
                       INPUT, OUTPUT,  AND  OPERATING PARAMETERS
Input Material
Characterization
total lead (S)
sulfur (S)
silica (S)
calcium (S)
moisture content (S)
density (M)
particle size distribution (M)
BTU value (S)
Furnace Performance
Parameters
test material in the feed (M)
air flow (M)
% oxygen enrichment (M)
fuel usage (M)
lead inputs (S)
iron inputs (S)
% test material in feed (M)

Furnace Output
Parameters
lead production rates (M)
slag production rates (M)
slag viscosity (0)
% lead in the slag (S)
% sulfur in the slag(S)
back pressure (M)
sulfur aioxide emissions (M)
calcium sulfate sludge (S)
                         (S)-Sample (M)=Measurement (0)=0perator Observation


 Furnace performance and output parameters were monitored through a combination of review of operators
 notes and logs, and direct observatipn by CHMR personnel.  In general,  production  data were obtained
 exclusively through operator logs, since that was  the only form available for the data. These logs are
 accurately kept and monitored by plant  management (who use the data for accounting purposes, and
therefore require accuracy).  CHMR  obtained copies of the logs when such data were to be used.

 2.5     QUALITY ASSURANCE/QUALITY CONTROL

 The project was conducted in conformance with the approved Quality Assurance Projed Plan  (QAPP),
 dated October 28,  1991.

 The QAPP  procedures related to several sets of parameters, including those listed in Table 3.  T h e
 analytical or measurement methodology  is also listed.
                                               10

-------
Some of the total parameters, including total lead, sulfur, iron, silica, calcium, were also determined  using
semiquantitative  emissions  spectrographic  methods, which  determined  an approximate concentration of
a wide range of compounds. These methods were employed when approximate measurements (±30%)
were sufficiently accurate, or as screening methods to determine  if a wide range of elements were present
in  a sample.

                                            TABLE  3
                           Methods Used  to Measure Test  Parameters
TYPE OF PARAMETER
Test Material Parameters






Furnace Perf. Parameters





Furnace Output Parameters






PARAMETER

Total lead
Total sulfur
Total Silica
Total Calcium
Moisture
Density

Percentage Test Material in
Furnace Feed (weight)
Air Flow to Furnaces
Oxygen Enrichment
Total furnace feed
Fuel Usage

Lead quality
Lead production rates
Slag production rates
Percent tead in slag
Percent sulfur in slag
SO2 Concentration in
Stacks
ANALYTICAL OR
MEASUREMENT
TECHNIQUE

SW 846 6010 (digestion 8
CP
ASTMD129-64 (digestion
&ICP
Spectrography
SW 846 71 40
Drying/weighing
Weigh known volume

Ratio of charges, density of
materials
Plant rotameters
Plant setting
Plant shift records/
observations
Plant ftowmeters

Spectrography (measure
impurity concentrations)
Plant shift records
Plant shift records
SW 846-60 10
ASTM D 129-64 or
equivalent
Plant CEM (calibrated
weekly)
Quality control procedures for  the  laboratory analyses included quality control both  within  and without the
analytical laboratory. For quality control within the analytical laboratory, CHMR reviewed  the laboratory
                                                11

-------
standard  procedures for conformance with  the standard analytical  methods.  These procedures called for
the use of periodic duplicates,  spiked samples, and blanks.

Quality control procedures outside the analytical laboratory related mainly to in-plant measurements. Many
of these  measurements were obtained from plant shift  data, which  are  presumably accurate. The
production data was corroborated where possible by CHMR  personnel observations - how many charges
of material were fed to the  furnaces during  a given shift? When was the furnace operating? How long did
they pour product or slag? These observations showed consistency between the numbers  obtained and
the practices observed.  For example,  over two shifts when CHMR  personnel noted a  30 percent reduction
in the number of charges fed to the furnaces, there was a corresponding  28 percent decrease  in the weight
of material fed to the furnace noted on the shift records, and a decrease in lead production of over 20
percent.   Based on these  observations, CHMR believes that the production  data were accurate to within
±10 percent.

Other observations, sutfur dioxide  emissions data, for example, were obtained from instruments which are
required by operating permits to be  maintained and  calibrated.  Although it was  not the focus of the study,
CHMR personnel noted no obvious deviations from those  requirements while  on  site.

Material density was obtained by weighing a known volume --typically a carboy - of material, and/or
weighing an entire truckload of material as it was dumped at the plant site. This  latter method was believed
to be more accurate, because the volume used could be determined based  on truck bed  size before the
material left the waste site and settled in the truck.  From analyses of the feed samples  from the Tonolli
study see Table  A-1),  CHMR found a range  of bulk densities of 23.2  to 28.4  Ib/ft3  (average  25.3  Ib/ft3)
using the  carboy method, and 23.7 to 31.4 Ib/ft3 (average 27.6 Ib/ft3) using the  truck weight measurement.
The overall average of  the densities was 26.7 Ib/ft3. The relative percent difference (RPD)  (calculated as
the difference between the duplicate  analyses divided by the average of the two values), between the
methods  of calculating was 8.7 %.

The most pressing  quality  control issues related to  the sampling. Battery case piles  are notoriously non-
homogeneous,  because the particles within them segregate both according  to density and particle  size.
In one early experiment, for example, CHMR obtained total lead concentrations  ranging between 3 and 16
percent.

To reduce errors  introduced by the  non-homogeneity, CHMR took  composite samples from  several areas
within a pile  (3 to 4).   In addition, the samples were often taken of the material as it was loaded onto the
truck for transportation to the smelter. This provided a more  representative sample  of material actually sent
to the smelter.

 During the NL  Industries study (Appendix B), CHMR obtained duplicate  analyses of eight input material an
slag samples between  two different  analytical laboratories  see especially Tables  B-1 and B-5).  The RPD
for  ead concentration  ranged between 0.9% and 42%, with  an  average  of 17.9%.

 Overall,  CHMR's  estimates of the total  lead concentrations and other parameters,  where  they are based
 on averages from several samples, are estimated to be within 20  percent of the actual value.
                                                 12

-------
                            3.0 RESULTS AND  DISCUSSION


In general,  the study demonstrated that various materials  may be processed in secondary lead smelters
witn relatively few effects on overall furnace  performance. The mpst  significant effects were caused by
processing  materials  in a furnace without property pre-processing it, or by processing  too much  material
at one time.  For example, the battery case pieces in the Tonolli feed were so large that they burned too
slowly in the reverberatory furnace, causing a  reduction in the furnace production rate. Later,  battery case
material from the Hebelka site was successfully  processed in the reverberatory furnace after it had been
shredded in a hammermill to a particle  size of less than 1/4-inch. The NL Industries material was  initially
unsuccessfully processed at 100  percent feed ratio because it was too dense for the feed system. When
the ratio of test material to total feed was lowered to  50 percent,  the  material  was processed with few
problems.

More extensive  summaries of the  evaluations from  these sites (NL Industries, Tonolli,  PennDOT, Hebelka
and HUD)  may be  found in Appendices  A through E, respectively.
3.1
PRODUCTION  PARAMETERS
The lead and slag production from the furnaces varied with each evaluation. Table 4 shows three lead and
slag production  parameters derived from the daily production of lead and slag at the smelter. The
demolition matenal evaluation is not included in Table 4 because this test was performed  primarily to
qualitatively determine if the  furnaces could process the light, wooden material.

                                           TABLE 4
                         LEAD AND SLAG PRODUCTION COMPARISONS

Furnace
Reverb
Blast
Parameter
Wt % Test Feed
% Pb in Test Feed
Pb Prod. Ratio
WL % Test Feed
% Pb in Test Feed
Pb Prod. Ratio
Pb Loss Ratio. /.„
Slag Ratio
Evaluation
Tonolfi
N/F
N/F
N/F
10%
3.5%
1.3
0.6
0.97
'Composition of bias
N/F means that the test mat
Hebelka
17%
14.7%
1.20
N/F
N/F
0.9
ft
1.00
NL Industries
20to50%
57%
0.90
30%
30%
1.25
1
0.97
PennDOT
N/F
N/F
N/F
13%
3.2%
1.1
2.6
0.97
slag was not analyzed
3rial was not fed to that furnace.
3.1.1  Lead  Production  Ratio

The Lead Production Ratio is the ratio of the amount of lead produced by the furnace processing test
material to that produced by the furnace  processing regular feed. This parameter can  be determined for
the reverberatory furnaces  only when the furnaces  are fed waste material,  but can be determined for the
blast furnaces in all cases,  since the blast furnaces indirectly receive the test feed  through the reverberatory
slag. A  value greater than 1  indicates that the furnace processing  the mix of test and regular feeds
produced  more lead than the control furnace.
                                               13

-------
The Ratios for all the other evaluations were different than 1, but not significantly so given the relatively
short durations of each  of the tests as compared to the three month ML  Industries  evaluation.

For the NL Industries material, the  lead production ratio for the reverberatory furnace is consistently below
1, averaging 0.9 over the three month period in which the materials were added to the furnace. However,
during the  same time period, the blast furnace associated with the "test'  reverberatory furnace produced
significantly more lead than its control counterpart. It appeared that the use of the test material  shifted the
production  of lead from  the reverberatory tp the blast furnace. This shift is attributed to the  relatively high
concentration of antimony and lead oxides in the waste feed material.  Antimonial lead and lead oxides melt
at higher temperatures than elemental lead, and are therefore more likely to be removed in the blast
furnaces, which operates at a higher temperature than the reverberatory furnaces.

3.1.2 Lead Loss Ratio

The secondary lead smelter  has two major outlets  for the lead input:  production and blast furnace slag
(waste).  The  Lead  Loss Ratio(Lp) Is the ratio of the loss of lead  in the slag from the test furnace (total slag
produced in the test furnace multiplied by lead concentration in that slag) to the loss of lead in the control
furnace. This ratio can only be calculated for the blast furnaces because the  blast slag is a waste  product
from the process. An  Lf, value greater than 1 means that more  lead  is lost in the blast slag produced  by
the furnace(s) processing test material than in the  control furnace(s).

The Tonolli evaluation produced  a much lower LRthan 1, while the value for the PennDOT evaluation was
2.6. The composition of the blast slag produced in the Hebelka evaluation  was not determined. The
apparent low value during the Tonolli experiment is most likely due to normal variatipns in the furnace
operations  and sampling  procedures, and it is not attributable to a significant increase in efficiency.
Over the course of tne  experiment with  the  PennDOT materials, the lead  concentrations  in the slag were
high and appeared to be climbing in both furnaces, even though the furnaces were not fed the same feed.
Therefore it is difficult to  determine  how significant the apparent increase in lead loss was. However, there
is reason to believe that some of the increased LR was due to the feed, since approximately twice as much
iron than is usually fed was added during the course of the experiment, and  additional iron binds lead to
the slag. Lead  concentration  in the slag  and quantity produced  when the  NL Industries site material was
processed  were  not different than when  typical feed was  processed.  Since this was the longest evaluation
in terms of time, this may show  that most material will have no  effect on furnace performance in  the long
run.

3.1.3  Slag   Disposal  Ratio

The Slag Disposal  Ratio (Sd is the amount of blast slag  produced by the test furnace  divided by the
amount of slag produced by the  control furnace. This is another term that is exclusive to the  blast furnaces
because reverberatory slag is  fed to the blast furnace, while the  blast slag is disposed.  In  all of the
evaluations, the S/^was effectively  1, which means the test and control  furnaces produced nearly equal
amounts of blast slag.

3.2     FEED RATIOS OF SUPERFUND MATERIALS TO TOTAL  FEED

Secondary lead smelters  normally accept feed materials derived  principally from the  breaking and
demolition  of lead-acid batteries. These normal feedstocks  consist primarily of lead grates,  terminals, and
sludge from the batteries. This material typically contains 60 to 70 percent lead, by weight with the
remaining  materials consisting of plastic,  rubber, wood scrap, sulfur,  dirt and  residues from the batteries,
and moisture  and oxides combined with the lead.  Superfund wastes and  other materials,  which contain
lower  concentrations of  lead and  higher  concentrations  of other  constituents that may  be  harmful to the
furnaces, must be blended with  "normal" feed  prior  to being led to the furnaces.

The mix ratio of normal  feed to waste materials was one of the parameters tested during  this study. Based
on  furnace performance  and operations results, it was possible to determine whether the furnace performed
successfully or unsuccessfully at any given feed ratio.  A test is considered to be unsuccessful if the feed
ratio of test material has to be lowered, or discontinued  altogether.

The tests show that the successful mix  ratios may be correlated with the  percentage of lead in the waste
material.  Figure 3  shows the feed ratios which were successful, plotted against the percentage of lead  in
the waste  material  (i.e.,  prior to blending with normal feed). The  results  are  nearly linear from streams
containing  3 percent lead to those containing 60  percent lead. This  delineates the region marked


                                                 14

-------
   100%  ,-
   80%  -
2
Q
UJ
UJ
Sb
o
ffi  60%
   40%
  • 20%
                         i UNSUCCESSFUL
                                                                 I UNTESTED
                                                                       SUCCESSFUL
    0%
       0%            10%          20%           30%           40%           50%           60%

                                        % LEAD W TEST MATERIAL


                      a SUCCESSFUL EXPEFUMENT    A UNSUCCESSFUL EXPEWMENT
                                           FIGURE 3
                   PERCENT LEAD IN TEST MATERIAL VERSUS FEED RATIO
the waste material (i.e., prior to blending with normal feed). The resujts are nearly linear from streams
containing  3 percent lead to those containing 60 percent lead. This delineates the region marked
"successful" on the figure. When the feed  ratios  versus  lead  concentration for  unsuccessful  runs  are
plotted, a second  region (the "unsuccessful"  area) emerges.  Finally, a third region, in which  no tests were
performed is also marked on the figure. No test feed with more than 60 percent lead was fed to the
furnaces, so the regions in the range  above  60 percent lead  cannot be determined  from the experimental
results.

It is important to note that the test results represent an empirical observation based on the tests performed.
Some of the correlation can be easily accounted for- lead concentration  affects density for example, and
material which is too dense is not easily conveyed into the furnaces, while material which is too tight will
fill up the furnaces and cramp out other feeds. Much of the correlation, however, is not easily accounted
for, and is simply based on furnace operator observations. CHMR believes that further study may help
delineate the  "untested" region, but that it may be more practical to simply perform  a treatability study on
a given feed  to more accurately determine the acceptable  feed  ratio.
3.3
       BENEFICIAL EFFECTS OF CERTAIN MATERIALS  ON  FURNACE PERFORMANCE
Some materials,  particularly  ebonite battery cases (which contain  coal or coke dusts), represent  a
potentially significant source of energy to the furnaces. The battery case materials had average BTU-
values of over 11,060 BTU per pound.  Coke is a typical feed to a blast furnace.  Ebonite rubber cases
were successfully  substituted for a portion of the coke in the blast furnace.  Battery cases will not substitute
for all of the coke  since the large chunks of coke provide structure inside the furnace, which battery cases
cannot  provide.
                                               15

-------
Other materials represent substitutes for other furnace feeds. Iron is typically fed to a blast furnace to help
separate  lead from the slag. The PennDOT bridge blasting material represented a source of iron and
calcium in the blast furnace. The  material contained so much  iron (over 60 percent) and so little lead in
comparison (approximately 3  percent), that it may  be  considered an iron source which happens to be
contaminated  with lead, rather than a lead source to the furnace.  In this capacity,  it represents a  pptentially
beneficial reuse for a material which most state and municipal authorities have found difficult to dispose.
This material would have to be added at a slower rate than  during the test run to be used as an iron
source

3.4    APPLICABILITY  OF  LEAD RECOVERY FROM  WASTE MATERIALS

 Broadly speaking, lead reclamation in secondary smelters  is an applicable technology whenever sufficient
 lead exists in a form which can be  economical retrieved from the Superfund  material. However, there
 are certain  materials, such as  materials  containing  large amounts of soil, In which the lead may not be
 easily reclaimed using the technology.  This  section describes the procedures to be used to  determine
 applicability and the range of applicability determined  by  the experiments.

 Generally, to determine if a material can be processed through a secondary lead smelter, a two step
 procedure is required: material characterization followed by  a pilot or treatability study at the smelter.
Table  5 lists the typical  parameters which must be  included in  a material  characterization. Not all these
 parameters were obtained or measured during the study:  many are based on requirements obtained from
the smelter.  Note that the smelter operators are not interested in the TCLP leachability of the  metals in
the waste, but the total metal content. The  leachability only determines the regulatory  status (hazardous,
 non-hazardous)  of the material,  and  does not affect its properties in a  smelter.

The table is intended to provide an approximate gauge of  the materials that can be processed through the
smelter. Because there is such a wide range of lead-bearing materials found in the environment,  it is
probably necessary to discuss a  particular waste feed with  smelter personnel before deciding whether the
lead is suitable for reclamation. Some wastes may be blended with other materials io make suitable
feedstock. A high calcium  waste, for example,  may be blended with other materials with little or no calcium
and fed to the furnace. Of course,  this blending may significantly increase the cost of storage and
processing. Other materials, such as metallic aluminum, are  prohibited in furnaces.

After  characterizing the waste material to determine its suitability in a smelter, a pilot-scale study may be
 necessary to better determine the effects on the furnaces and the appropriate operating  parameters. These
will likely have significant bearing on the economics of treating the material.  The demolition material tested
 during this study, for example, had to  be shredded and blended  relatively slowly with normal  furnace feed.
 This increased the handling and storage requirements by more than 50 percent. A more detailed cost
 analysis is presented  later in this paper.
                                                 16

-------
                                           TABLE 5
                        REQUIRED  CHARACTERIZATION
                                                  PARAMETERS
Constituent
Total lead
Total antimony
Total arsenic
Total copper
Total halogens
Total tin
Total iron
TCLP - metals
Physical state
Total sulfur
Total silicate
Total soil content
Fuel value (BTU/lb)
Total calcium
Total aluminum
Particle size
Oil and Grease
Moisture
Density
Ash content
(excluding lead)
Lower limit (If
applicable)
1%
NA
NA
NA
NA
NA
NA
NA
No liquids or
gases
NA
none
none
none
none
none
5 microns
none
none
none
none
Upper limit (If
applicable)
100%
NA
2%
2%
<1%
2%
none
NA
No liquids or
gases
10%
20%
25%
NA
10%
1%
I m
<2%
15%
none
70% (est.)
What does parameter affect?
Economics (based on lead
recovery), feed rates
Needed to determine refining
requirements
Lead quality, refining
Lead quality, refining
Damage flue gas system, permits
Lead quality
Feed rates (iron is a furnace feed)
Overall need to process
Conveyance, furnace performance,
permits
CaS04 sludge production, sulfur
emissbns
Furnace performance
Furnace performance, economics,
slag production
Economics
Furnace performance, feed ratios
May cause explosions in the
furnaces
Loading, conveyance
Permits, feed system, material
handling
Heat requirements, may cause
steam explosions
Loading, conveyance, economics
Slag production, furnace
performance, economics
3.5
LEAD  RECLAMATION  EFFICIENCY
In determining whether the process is  suitable for  Superfund activities, it is important to determine if the
secondary lead smelting process actually  reclaims  lead from the various  materials. Unfortunately, there
was no way to precisely measure the extent to which the lead from the Superfund materials is reclaimed
after these materials  are mixed  with regular furnace feeds.  Therefore,  a methodology  was developed to
estimate the minimum reclamation efficiency based  on conservative assumptions regarding the  partitioning
of lead inside the furnaces.
                                               17

-------
Generally, lead inputs to the smelter include feeds to the reverberatory and blast furnaces. During  normal
smelting  operations,  outputs from the smelter include [29]:

               Lead production from both furnaces (usually  between 99.5 and 99.7 percent of the lead
               feed);

               Blast furnace slag (which contains 0.3 to 0.5  percent of the lead feed);

               Calcium sulfate sludge from the emissions control system (which contains approximately
               0.004 percent of  the lead feed); and,

               Fugitive and  stack air emissions (which contain less than 1CT5 percent of the lead feed).

The furnaces reclaim over 99 percent of the  lead fed to them. The only  significant  outlet for lead  besides
lead product is the slag, which must be landfilled. For the purposes of  estimating reclamation efficiency,
the slag may be estimated to contain 1.5 to 2 percent lead,  which the literature suggests can be maintained
over a variety of operating conditions [30].

The minimum  reclamation efficiency can be estimated noting that the lead partitions between the  lead
product,  which is essentially pure lead, and slag, which contains 1.5 percent (by weight) lead. The
percentage  of any feed material partitioning  to the slag is approximately equal to the  concentration of non-
lead,  noncpmbustible materials in the feed  (which is approximately equal to the ash content minus the lead
concentration in the feed). Thus, for test  material with a measured ash  content of 50  percent,  and 30
percent lead, it Is reasonable to assume that the remaining 20 percent of the feedstock will  become part
of the slag.  If we further assume that the slag produced by Superfund materials is indistinguishable from
that produced  by normal  feeds operating under the same furnace conditions, and therefore will contain the
same weight fraction of lead as the slag normally contains, then we can  estimate the amount of lead from
the Superfund material lost with the slag. This can be compared with the original amount of lead in the
Superfund  material  to determine  a reclamation  efficiency:

                                    e =  1 - [PbJ ([A] - [PbMPb]

where  e  is the minimum reclamation efficiency; [Pb?]  is the  lead concentration in the slag; [A] is the ash
content of the test material (as a weight fraction); and [Pb] is the weight  fraction  of lead in the feed. Based
on this estimate, the minimum reclamation efficiencies for the various feedstocks  used during the
experimental program ranged from a high of 99.5 percent for the Pedricktown material with 45 percent lead
and 60 percent ash  content, to a low of 10 percent for the PennDOT material,  with an ash  content of 70
percent,  a  lead content of approximately 3  percent,  and a lead concentration in the slag of approximately
4%.  (Note that the lead concentration  in the slag was  especially high dunng the time that the PennDOT
material  was run for  reasons which appeared to be independent  of the PennDOT feedstream. The lead
reclamation efficiency would normally be  considerably higher.) The results show that  lead reclamation
always occurs, even  when minimum reclamation conditions are  assumed.
                                                 18

-------
                         4.0 LEAD  RECLAMATION  ECONOMICS


The cost of using secondary lead  smelters for the recovery of lead from Superfund sites is determined by
the cost of the three basic operations:

                On-site excavation and  preprocessing of the material (CE)
                Transportation  (CT)
                Processing  at the smelter (CP)

These costs  are  discussed in further detail  below.

4.1     ON-SITE EXCAVATION

Excavation costs for Superfund  materials vary depending on the health and safety requirements  for given
sites,  contaminants and contaminant concentration. For battery  cases, or lead debris, dross, etc., which
are relatively accessible on the site,  and require little more than dust control during excavatipn, the costs
range between $5 and $15 per cubic yard.  On-site costs, denoted as CE, will Increase if additional on-site
processing is  required.

4.2     TRANSPORTATION

Transportation  costs for hazardous wastes are dependent on  the amount of  material  transported, and the
distance transported. Typical  costs range between $0.20 and $0.35  per ton-mile (transport 1 ton  1 mile).
For  most material, the cost  of transportation, CT, is estimated as:

                                          Cy = $0.3 D/mile

where D is the distance from the site to the smelter in miles. Note that for longer distances (over 300
miles), alternate means of transportation  (i.e. tandem trucks, rail shipment, etc.) may  be more economical.


The  transportation economics shift  slightly for  some materials, particularly those with specific  gravities
significantly less than  1. These  materials  may include whole (i.e., uncrushed)   battery cases which, because
of their structure, have relatively  large void volumes and therefore a low density. Unless these  materials
are  crushed  on-site, the transportation costs will be based  not on their weight but on their volume.  This
will necessitate a correction factor  on the transportation  cost equation w'nich  is equal to the inverse of
the  material bulk density in ton peryd^, and a maximum of 1. Thus, the overall transportation cost can be
estimated  as:

                                            CT = 0.3 
is equal to max (1/p,1), in which p is expressed in dimensions of ton per yd.3 4.3 PROCESSING AT THE SMELTER Based on the results of the study, processing costs for the materials vary significantly depending on the concentration of lead, the market price for lead, and the percentage of the feed which becomes slag. As the market price for lead or the concentration of lead in the feed material decreases, the cost of processing Superfund materials will increase, because the lead represents a salable commpdity generated during the reclamation. If the material contains a greater fraction of constituents which exit the furnace in the slag fraction, then the cost increases commensurate with the disposal costs of slag. Most of the other parameters (for example, a slight increase in oxygen usage in the furnace) have little overall affect on the cost of processing. CHMR has developed a model for estimating the costs associated with processing Superfund materials at a smelter. The model breaks the cost into four major categories: a base cost (per ton) to cover a portion 19

-------
of normal smelting costs,  additional production costs specific to the material, additional disposal  costs, and
offsets of the value of the recovered lead and reductions in other feeds (if any) to the furnace. These are
described further below.

4.3.1    Base Cost CB

According  to the literature [12, 17, 27, 29] the cost of processing material  in a smelter  is approximately
$0.10±0.02 per  pound or $200± 40 perton of material processed.  Note that this is not the cost of
producing  a pound of lead which is typically estimated at between $0.12  and  0.17 per pound, but is the
cost of processing a  pound of feed.  The two are  related, since furnace feeds  [including  coke, iron and
limestone]  contain  55 to  65 percent  lead. This cost  includes the  cost of handling and loading the material,
maintaining the smelter,  normal furnace inputs (coke, natural gas, oxygen, etc.), labor costs, environmental
compliance costs,  etc.

4.3.2   Additional  Production Costs

These  costs include additional  labor and equipment  costs associated with  handling an atypical feed at the
smelter. Included in  this category are costs  associated with maintaining  a staff member on-site during
loading to ensure that the proper materials are loaded onto the trucks (estimated at $6 per ton); labor costs
asspciated with inspecting, unloading, and mixing the material at the  smelter ($10 perton); costs for
additional  management  time and attention for the material  ($3 per ton); additional capital costs at the
smelter, including loading equipment,  storage areas, and  piloting costs  (estimated  at $18 perton); legal and
contractual costs associated with handling Superfund  materials ($10 per ton);  and miscellaneous costs,
such as  analytical  costs  (estimated at  $10 per ton).  These  additional production  costs  remain  relatively
fixed independent of the  amount or types of matenals  processed, at $60110 per ton.

For light materials, the additional  processing costs will be based on their volume,  rather than weight. More
than likely,  however, the  smelter will choose to crush or grind them before feeding them to the furnaces,
at a cost of between  $10 and  $15 per cubic yard. To denote this, a  correction  factor T = $15 per ton is
applied when the bulk density of the  matenal is below 0.8 tons per yd3. If the density is above 0.8 tons  per
yd3, «F= 0.

4.3.3   Additional Disposal Costs Cdisp

Additional  disposal costs  associated with  processing Superfund materials  include  the disposal of slag and
calcium sulfate  sludge.  Based on measurements taken at the smelter, CHMR determined that typical
smelter feeds produce in the range of 200 Ibs  of slag per ton of feed  10 percent slag in the feed), and  60
Ibs of  sludge per ton of feed (based on 3 percent sulfur in  the feed).  This material is typically disposed of
at a cost of $150 perton. The cost to dispose of 200 Ibs of slag and 60  Ibs of sludge is included above
as part of  the overall cost to process the material.  However, some Superfund and waste  materials may
contain significantly  higher  percentage of compounds which  will end  up  in the slag, or sulfur which will
produce  sludge. Therefore, the overall  processing cost  must be adjusted to include the cost to dispose of
the waste  materials  produced  by the feed. This adjustment is calculated  as:

                              Cdisp= $150 ([N] - 0.1) + $100 ([S] - 0.03)

where [N  represents the  percentage of non-combustible,  non-lead, and non-volatile material in the
superfund material, and [S] is the  sulfur content of the feed.  [N] can then be calculated by:

                                          [N] = [A] -1  .1  [Pb]

where [A] is the ash content of the waste material, measured at or  above  1500°F, and [Pb] is the
percentage lead in the material. The correction  factor to the  lead concentration corrects for  the appearance
of lead oxides in the lead. The overall disposal cost differential is therefore:

                                Cdisp = 150[A] - 165 [Pb] + 100 [S] -  18.

 4.3.4    Offsets for the Value  of Lead  and Reduction of Other Furnace  Feeds

 The value of the recovered lead in  a  waste material is given by:

                                           CPb= - e, P [Pb]


                                                 20

-------
where Er is the  reclamation efficiency for the feed in question (assumed to be approximately 1), P is the
market price for  lead in dollars per ton and [Pb] is the weight fraction of lead in the material.  The negative
sign on the cost indicates that this is not a "cost" per se, but in reality a  credit for the  lead content to the
smelter. The January 1994 market price for lead was approximately $700 per ton. This is down from over
$750 per ton in 1991, but up from  $450 per ton in 1992. The volatility in the price of lead is due to large
sales of lead from the former Soviet Union and the price is  anticipated  to stabilize  during 1994 [32].

A second benefit from Superfund materials is decreased coke usage. For materials such as battery cases,
which  can  be essentially  a supply of coke to the furnace, the  change in required coke is related to the heat
value  of the Superfund materials (which in this discussion will be denoted by  [BTU]  and given  in units of
 BTU per pound). If coke  were used only as a  fuel source inside a furnace, and  if the  battery case materials
 burn similarly to coke, then the reduction in coke usage based on addiiion of a Superfund  materials would
 be equal to the  ratio of the BTU value of the Superfund material to that  of coke (i.e., if you feed 1 BTU of
 energy to the furnace from the Superfund material, you would save 1 BTU's worm of coke in the furnace).
 However, coke is not used only as a fuel source,  but also to provide structure to  the materials inside the
 furnace.  In addition, battery cases, with different sizes and shapes, do not burn at the same relativity
 homogenous rate as  coke input to a furnace. Therefore, a one-to-one  reduction in energy supply between
 Superfund materials and coke is not possible.  Based on the reduction in  coke requirements for the Tonolli
feed, in which a 10 percent feed of a material with a heating value of 12,000  BTU per pound  allowed for
 a reduction of 30 percent in  the coke usage, CHMR estimates that approximately 25 percent of the heat-
value  of a Superfund waste  can be supplied to offset the blast furnace  requirements for coke. Based on
this, the BTU-value of coke (13,000 BTU per pound) and the  market price or the coke used in the furnace
 (approximately $150 per ton), the cost savings from the BTU-value of the Superfund material can be
 estimated  as:
                                    Ccoke=  - 0.007 ([BTU] - 2000)

where Ccoke is in terms of dollars per ton of feed material. The cost savings include savings from not having
to add the coke as part  of the base feedstock to the furnace. The 2,000 BTU per pound differential in  the
 equation is included  because below a minimum level, the material probably provides  no  realizable benefit
to the furnace,  and may even increase fuel  requirements because of its thermal  capacity.

 Likewise,  the content of a  Superfund material may provide significant benefit to the  furnace.  The
 extent of reduction allowed by the addition  of Superfind materials containing iron could not be  estimated
from the experiments conducted, because the smelter fed the material  at a rate  significantly higher than
they usually feed iron. However, assuming  a 75 percent tradeoff from  metallic iron input to the furnace,
 and based  on the market  price  of scrap iron ($130 per ton),  the potential cost avoidance savings are:

                                     CFe=-360 max ([Fe]-0.1,  0)

where [Fe  is the weight fraction iron in the  feed.  Note that the equation predicts that there is no  benefit
 if the  iron fraction is below 0.1. The formula includes a correction to avoid double counting the  iron  which
 needs to be disposed.

Thus, overall cost benefits and avoidance CA based on the lead in the Superfund material and  reductions
 of coke and iron  usage  is:

                     CA= - P [Pb] - 0.007 ([BTU]  - 2,000) -  360 max([Fe] - 0.1,  0)

 with [BTU] in BTU  per  pound  and [Fe] as weight  percentage metallic iron in  the feed,  and the lead
 reclamation efficiency assumed to be 1.

4.3.5   Net Smelter Processing  Cost

 The net cost to process  the  waste materials  in a secondary  lead smelter, is therefore:
                     Cp = 256 + 150 [A] -^65 1 P) JPbl -t 100 [S] - 0.007 [BTU]
                                        360 max([Fe]- 0.1,0)

where Cp is in units of dollars per ton of material.
                                                 21

-------
4.4    OVERALL  PROCESS  ECONOMICS

 The  overall  process economics can be  determined by combining  the  various components  (excavation
 transportation, and  processing the materials):
 where Cyrt is the overall cost of processing in dollars per tpn.  Fixing the cost of excavation and required
 pre-treatment at $15 per ton, inserting a function of distance (D)  from the smelter  (in miles) for
 transportation costs,  and combining the processing cost for the  material,  C^ becomes:

                      CTot= 271 + 0.34>D + ¥ +  150 [A] + 100 [SI-  (165  + P) [Pb]
                                 - 0.007  [BTU] - 360 max([Fe] - 0.1, 0)

 with  Cjot in dollars per ton of material. [A] is the percent  ash content of the waste material;  [S],  [Pb], and
 [Fe are the  percent sulfur, lead, and iron concentrations, respectively.  [BTU]  is  the heating vaue in  BTU:
 an   P is the price for lead in dollars per ton.

 Correction factors $ and ¥ are functions of the bulk density of the material (in ton per yd3) where * = max
 [1/ p, 1) and ¥ = 0 if p> 0.8 ton per yd3 and $15 per ton if p 5 0.8 ton per yd3.  Neither correction factor
 will likely  apply if the material is crushed  on-site  to increase its density  and decrease handling costs  before
 being snipped to the smelter, but, of course, the cost of this crushing must then be added to pre-processing
 and  excavation costs.

 Based on this cost model, the overall cost of processing the materials from the sites studied during this
 research,  have  been  calculated, and are presented in Table  6. The table includes two costs,  the first based
 on a conservative market price for lead ( 650  per ton) and the second  based on a more plausible long-term
 cost for lead ($750 per ton). Npte that the overall cost  of using  secondary lead smelters as a treatment
 technology for Superfund sites is dependent on  the  lead content and  market price for lead and total ash
 content (i.e., slag generation potential) of the material.
                                              TABLE 6
                                   COST OF REMEDIATING  SITES
Site
Tonolli
Hebelka
Demolition Material
NL Industries
PennDOT
P=$650/t
Cost/ton
$228
$174
$374
$80
$231
P=$750/t
Cost/ton
$224
$160
$373
$35
$228
Distance
D (miles)
40
75
100
200
250
%Ash
[A]
20
30
4
65
70
% Lead
[Pb]
3.5
14.7
1
45
3.2
                                                 22

-------
                                     5.0 CONCLUSIONS


Lead is a common contaminant at Superfund sites, present at between 30 and  50 percent of the sites, and
reclamation is one viable option for remediating the sites. The following conclusions may be drawn from
the study of reclamation of lead from Superfund sites using secondary  lead smelters.


        Lead was successfully  reclaimed in a secondary lead sme|ter from a variety of materials, including
        battery case pieces,  dross, lead  debris, spent  abrasive materials, and  demolition material
        contaminated with lead paint. The lead concentration  in these materials ranged form  1 to 45
        percent.

        The economics of reclaiming lead from  Superfund  sites are dependent on lead concentration, the
        market price for lead, distance from the smelter, the amount of  materials which become
        incorporated  into slag  from the  process, iron content, BTU-value  of the wastes,  and to a lesser
        extent,  sulfur concentration.

        The cost for recovering lead from the five sites selected for this project, based on a conservative
        price for lead ($650/ton), ranged between $80 and $374  per ton of materials.
        The Superfund  material must generally be mixed with regular furnace feed prior to being
        processed. The acceptable weight  ratios  of the  Superfund  material to overall furnace feed
        Superfund plus  regular materials) were found empirically to be a function of percentage lead in
        ' ie Superfund  materials, with the  approximate linear function: Mix ratio = 0.1  +  0.5[Pbfeed], where
        [Pbfeed] is the concentration of lead in  the  Superfund  material.
£
th
Overall, CHMR concludes that  secondary lead  smelters provide a viable alternative  to stabilization and
disposal for the treatment of wastes found at battery breaker and secondary  lead smelter Superfund sites,
as well as for other commonly  found  lead-containing waste streams.

Factors in selecting  reclamation using secondary lead smelters for the materials found at  Superfund sites
include:

       Lead concentration;
       Material type (dross, debris, slag,  soil, etc.);
       Density of the material;
       Sulfur,  calcium,  iron, antimony, soil,  aluminum, and  silica concentrations;
       Moisture  content (smelters generally cannot accept wet  materials);
       Presence of organic wastes,  haiogenated  materials, and gaseous  materials  (which typically are
        prohibited in smelters); and,
        BTU-value.

In all cases,  a  thorough analysis of the site materials is anticipated to be necessary before the material is
accepted.  In some cases, a treatability study to determine the allowable mix ratios and effects of the
material on the furnaces may be necessary before a stream is accepted by the smelter.
                                                23

-------
                         6.0 RECOMMENDATIONS  FOR LEAD
                     RECLAMATION  AS A REMEDIAL APPROACH

Table 7 provides a comparison of the use of secondary lead smelting to other remediation technologies
described in the paper for a variety of feeds. The table includes all costs associated with processing each
feed in the technology indicated. The table shows that secondary smelting is the most economical
alternative  for lead debris,  and competitive for battery cases.

Secondary lead  smelting has other advantages over the alternative  technologies, including:

               It is a permanent solution - The lead is reclaimed and put back to its original use. The
               long term effects of other technologies, such as  landfilling or stabilization, are still
               uncertain.

               It reduces liability - Once the material is processed in the smelter, it is no tonger a waste,
               but a product permanently ending the long  term  CERCLA  liability of disposing the waste.

               It uses existing  technology - This eliminates  the need to  develop mix ratios for solidiiition
               or stabilization

               Smelter receptivity -  In a limited informal survey, CHMR found that virtually all secondary
               lead smelters are permitted  to accept  lead-containing hazardous wastes, and that
               approximately  half were amenable to doing so.

CHMR estimates that the total amount of battery case material and other debris which could be processed
annually in the U.  S. secondary smelters is approximately 300,000 tons. This is based on 25 tons per day
per furnace,  and 280 production days per year. It appears at this point that several U. S. smelters are
currently planning  to accept Superfund materials.


                                          TABLE 7
                  COMPARISON OF SMELTING AND OTHER TECHNOLOGIES
Technology
Stabilize/Capping
Stabilize/Disposal
Physical Separation
Extractive Washing
Secondary Lead
Smelting
Media Price Range/ton
Soils
Battery Cases
Soils
Soils
Battery Cases
Soils
Battery Cases
Battery Cases
Debris
Other Materials
$30-100
$50-150
$50-200
$60-200
$60 250
$60-250
$75 - 300
$100-250
$60-200
$100-300
Comments
Limited application

Process + dispose
Metal Recovery
Metal Recovery
                                              24

-------
                                     7.0  REFERENCES


 1.      E. Earth and R. Soundararajan,  "Solidification/Stabilization Treatment of Lead Battery Site Soils,"
        HMCRI Superfund '90 Conference, Hazardous Materials Control Research Institute,  Greenbelt,
        MD, 1990, p. 665.

 2.      P. Watts, C. Pryately and J. Gormley,  'Characterization of Soil-Lead Contamination at an NPL Site
        Using a Combination of Field Screening and Laboratory Analytical Techniques," HMCRI Superfund
        '91  Conference  Hazardous Materials Control  Research  Institute, Greenbelt, MD, 1991, p. 498.

 3.      J. Swartzbaugh, et al., "Remediating Sites Contaminated With Heavy Metals,  Parts I and II,"
        Hazardous  Materials Control, November/December 1992, p. 36, and March/April 1993 p. 51.

4 .      M.  Royer, A. Selvakumar, and R. Gaire,  "Control Technologies for Remediation of Contaminated
        Soil and Waste Deposits at Superfund Lead Battery Recycling Sites," J. Air and Waste
        Management, Vol 42,  No. 7,  1992,  p.  970.

 5.      A.Y. Lee, A. Wethington, and  M. Gonnan, "Treatment of Lead  Wastes from Lead-Acid  Battery
        Recycling Plants," EPD Congress 1993, J. Hager (Ed.), The Minerals, Metals  and  Materials
        Society, Warrendale  PA, p. 927.

 6.      W.E. Fristad, "Terramet Lead Leaching and Recovery at an Arm Ammunition Facility," Emerging
        Technologies In  Hazardous Waste Management V, Tedder Ed.), American  Chemical Society
        Industrial & Engineering Chemical Division, 1993, GA, p. 513.

 7.      R.J. Schmitt, "Automobile Shredder Residue - the Problem and Potential  Solutions,"  Recycling
        of Metals and Engineered Materials,  J. Linden et al  (Eds.), The Minerals, Metals and Material
        Society, 1990, Warrendale PA,  p. 315.

 8.     J.L. Hessling et al., "Results of Bench Scale Research Efforts to Wash  Contaminated  Soils at
        Battery Recycling Facilities," 2nd International Symposium on Metals Speciation, Separation
        and Recovery, Rome Italy, 1989, p. 183.

 9.     A.  Saracino and C. Parent, "Soil Washing of Lead-Contaminated  Soil at a Former Gun Club Site,"
        Wallace-Kuhl & Associates, West Sacramento, CA,  1992.

 10.     E.R. Krishnan and R.J. Turner,  "Overview of Metals Recovery Technologies for Hazardous Waste,"
        National Research  & Development  Conference on Control of  Hazardous Materials HMCRI,
        1991.

 11.     S. Paff, "Using Secondary Lead Smelters for the Recovery of Lead from Rubber Battery Cases and
        Other Materials," Center for Hazardous Materials Research, Pittsburgh, PA, 1992.

 12.     W.F. Kemner  and  E.R. Krishnan, "Electromembrane Process for Recovery of Lead from
        Contaminated Soils," Innovative Waste Treatment Technology Series, 1990, p. 87.

 13.     R.S. Simms and K.  Wagner, "Treatment Technologies Applicable to Large  Quantities of Hazardous
        Waste Contaminated Soils," USEPA  Municipal Environmental Research Laboratory Cincinnati, OH,
        1991.

 14.     T. Scherer and D. Gillette, "Affordability Analysis of Lead Emission Controls for a Smelter-Refinery",
        EPA Control Technology Center, Research Triangle Park NC, 1989.

 15.     W. Urban and  S. Krishnamurthy,  "Remediation  of  Lead  Contaminated  Soil,"  Foster Wheeler
        Enviresponse, Edison, NJ, 1993.
                                               25

-------
 16.    A. Davis, M. Ruby and P. Bergstrom, "Geochemical Controls on the Bioavailability of Lead from
        Mine Waste Impacted Soils," HMCRI Superfund '91 Conference, HMCRI, Greenbelt, MD,  1991,
        p. 564.

 17.    S. Griffin, "Application of USEPA's Uptake Biokinetic Model for Establishing Soil Lead  Cleanup
        Levels at Superfund  Sites," HMCRI Super-fund '91 Conference,  HMCRI,Greenbelt, MD, 1991
        p. 495.

 18.    Center for  Hazardous Materials  Research, 'Site Characteristic  Profile Study and Competitive
        Technology Analysis," May, 1991.

 19.    M. Royer  and T. Basu, "Selection of Control  Technologies for Remediation of Lead Battery
        Recycling Sites,' EPA Risk  Reduction Engineering Laboratory, Edison, NJ, 1991.

 20.    T. deGrood, "Appeal of stabilization,  solidification grows for treating  wastes,  HazMat World,"
        February, 1991, p. 60.

 21.     USEPA, "Solidification/stabilization of organics and inorganics,"  Engineering Bulletin, EPA/540/S-
        92/015,  May,  1993.

 22.    D.S. Schleck,  "Treatment, When Does It Apply?." HMCRI Superfund '90 Conference, HMCRI,
         1990, p. 677.

 23     M  Royer  "Selection of Control Technologies for Remediation of Lead Battery Recycling Site
        Wastes,' USEPA Engineering Bulletin, EPA/540/S-92/011, 1992.

 24.     D.R. McCombs, "Operating a Hazardous Waste Landfill, HazMat World, September, 1991,  p. 73.

25.      R. Gager, "Hazwaste Landfills Struggle for Growth and Safety," HazMat World June, 1991, p. 46.

 26.     Center  for  Hazardous Materials  Research, 'Acid Extraction Treatment System for Treatment of
        Metal Contaminated  Soils," September, 1993.

27.      H. Masters and B. Rubin, "EPA's Mobile Volume  Reduction Unit for Soil Washing,"  USEPA's RREL,
         Proceedings  from the 7th Annual RREL Hazardous  Waste  Research  Symposium,  Cincinnati,
         OH, 1991,  p. 89.

 28.     Brice Environmental  Services Corporation, "Qualifications  for Soil Washing Services," 1992.

 29.     R. Coleman and R. Vanndervort, "Evaluation of Paul Bergsoe and Son Secondary Lead Smelter,"
         USEPA Office of Research and  Development,  EPA-60072-80-022, 1980.

 30.     P. Queneau, D. Cryar, and D. Mickey, "Optimizing Matte and  Slag Composition in Rotary Furnace
         Smelting of Lead Residues," Primary  and Secondary  Lead Processing, Jaeck  (Ed.),  The
         Metallurgical Society/Pergammon Press, New York, 1989.

 31.     R. Isherwood et  al.,  "The Impact of Existing and Proposed Regulations Upon the Domestic Lead
         Industry," U.S. Bureau of Mines, Denver, CO,  1988.

 32.     P. Queneau  and A. Troutman, "Waste Minimization Charges  Up Recycling  of  Spent Lead-acid
         Batteries," HazMat World, August, 1993, p. 34.

 33     A.D. Zunkel  and J.C. Taylor, "Integrated Primary/Secondary Lead Smelting," Journal of Metals,
         January, 1988,  p. 32.

 34.     Center for Hazardous Materials Research, "Quality Assurance Project Plan  and Work Plan for
         Using Secondary Lead Smelters for the Recovery of Lead from Rubber Battery Cases and Other
         Waste  Material,"  October,  1991, pp. 6-11.

 35.    Personal correspondence between the author and Charles Faust of Earth Treatment Technologies
        (Dutton  Mill Industrial Park, 396 Turner Way, Aston, PA 19014,  February 1994).
                                               26

-------
                    APPENDIX A
RECLAMATION OF MATERIALS FROM BATTERY CASE PILES
         AT THE TONOLLI SUPERFUND SITE IN
                 NESQUEHONING, PA

       Description of Evaluation and Results and Discussion
                     July 23, 1992
                        27

-------
                          1.0  DESCRIPTION OF  EVALUATION


The purpose of the evaluation was to determine the feasibility and economics of the recovery of lead from
battery case materials.  The Tonolli Corporation Superfund site in  Nesquehonina Pennsylvania  was used
as the source of these materials. The materials were processed at Exide's Reading,  Pennsylvania,
secondary lead smelting facility.

Exide's Reading  smelter is primarily engaged in recycling lead from lead-acid batteries,  such as those
utilized in  automobiles and the recycling of polypropylene rom battery cases for subsequent reuse.  Exide
uses both reverberatory and blast furnaces to recycle lead. These furnaces and other plant operations are
typical of  the secondary lead smelting industry.

This appendix incjudes a description of the evaluation, and a discussion of the results. The conclusions
from this  evaluation  have been  ncorporated  Into those found in  the main body of this report.

1.1       EXPERIMENTAL  DESIGN

During the evaluation, the material from the Tonolli site was fed to both the reverberatory and blast
furnaces.  Initially, the test material was fed directly to each furnace using a front-end  loader, which loaded
one toad of test material, then several |oads of regular feed (depending on the  mix ratio), then another bad
of test material, and so on. However, it became apparent that the furnaces would  better  handle the test
material if it were initially mixed with the regular feed, and the  resultant mixture charged to the  furnaces.

The plant is  equipped with two blast and two reverberatory furnaces.   Generally one reverberatory furnace
and one blast furnace were  utilized for processing the Tonolli material, which the second  reverberatory
furnace and blast furnace remained  in normal, routine operation. Conducting the test in this manner
allowed for comparison of the operation of the lest" furnaces with the "reference"  or "control" furnaces.

During  the  evaluation, the operating  parameters (fuel  usage,  oxygen usage,  slag production, lead
production,  etc.)  for each set of furnaces were obtained. In  addition, samples of slag and  lead were
obtained from  each furnace to be used to determine effects  on production quality.

1.2     CHRONOLOGY OF EVALUATION

The following represents a  chronology of the activities conducted  in support of the evaluation, between
September Sand 13, 1991.

1.2.1     Material  Acquisition  and Sampling

On September 5, 1991, five  dump trailers of material were loaded with battery case materials from the
Tonolli  Superfund site in Nesquehoning, Pennsylvania.  Because the battery case materials were  stored
in piles at the Tonplli site and no separation of materials was necessary, no problems were encountered
during loading activities. No dusting problems were encountered  during loading activities. A total of
 167,750  pounds of material  was transported in five dump trailers, ranging from 42 to 48 cubic yards of
 material per trailer.

Composite samples of each battery case pile  were  collected during the loading process at the Tonolli site.
The samples  were subsequently analyzed to determine:

                 bulk density;

                 percent of the hard rubber material in the total sample;

                 percent of polypropylene plastic in the total sample;

                 percent of other miscellaneous material (i.e. soils, concrete, etc.);
                                                28

-------
                    percent of metallic lead in the total  sample;

                    lead concentration using the Toxicity Characteristic Leaching Procedure (TCLP) on rubber
                    cases;

                    total sulfur;  and

                    percent of lead contained in the rubber, soil,  concrete, etc.

The analytical results of this material are presented in Table"! A-1. A discussion of these results appears
later in this report.

1.2.2  Major  Activities

This section describes the major activities that occurred during this evaluation. These activities are
presented chronologically  starting with the  first day of processing  through the smelter.

Day One

Activities completed during the first day of the test included density determination of test material, which
was determined by weighing trucks as they entered and  exited the plant, and dividing by the truck bed
volume.  One blast furnace was charged  at a 7 percent test material  feed ratio  and one  reverberatory
furnace was charged  at an  11 percent feed  ratio, in  accordance with  the  QAPP. The test material feed
ratio is calculated  by dividing the weight of "test" material charged to the furnace by the total weight of feed
(including "test'  material and typical feed).

Day Two

Early in the second day, both blast  furnaces were running sluggishly and there  was a crust accumulating
within the reverberatory furnace which was being charged with test material.  Based  on the amount of coke
added during the previous night, the plant  management concluded that the blast furnaces were overcoked.
This was unrelated to  the evaluation, but  Exide management still  decided that it would be  best to refrain
from charging additional test feed to the blast furnaces until the build up within the furnaces was reduced.
The accumulation  of the crust in the reverberatory furnace was determined to be related to the  experiment.
Therefore,  test feed input to that furnace was suspended.
                                                  29

-------
                                                           TABLE A-1
                                         ANALYTICAL RESULTS FROM TEST  MATERIALS
Sample
1
2
3
4
5
6
7
8
Type of Sample
Composite from trucks
taken at site
Composite from trucks
taken at site
Composite from trucks
taken at site
Composite from trucks
taken at site
Composite taken at
smelter
Composite taken at
smelter
From piles on site
From piles on site
(duplicate of 7)
Bulk
Density
(lo/ty
24.4
23.2
I6.9*
28.4
•^
™
— '

Hard
Rubber
(wt%)
76.3
70.7
67.9
79.9
~
—
—

Plastic
(wt%)
22.5
27.8
27.5
18.0
—
—
—
•~
Concrete
Soil, etc.
(wt%)
1.0
2.6
2.6
2.0
— -
-—
—
3.0
Sulfur
(wt %)
3.10
_t
.•••
—
1.93
2.71
—
—
Metallic
Lead
(wt%)
0.25
0.05
0.05
0.10
—
~
—
0.10
Total
Lead
(wt%)
0.34
0.82
0.47
1.57
15.7
7.3
1.15
0.28
TCLP
Lead
(mg/L)
130.9
111.8
131.3
159.4
™~
•—
—
—
                                 * Value was found to be anomalous by q-test at 90% confidence limit

Notes: Samples 5 and 6 contained notipeable quantities of reddish sludge, which apparently was a lead oxide compound. Therefore the total lead
      concentration In these samples is  significantly higher than those for other samples.

              Additional  bulk densities were calculated by obtaining weights and volumes from the trucks. These were calculated to be: 29.,
              27.3, 23.7, 31.4 and 26.6  Ib/ft3 respectively on trucks 1 through 5. The overall  average of all the values  obtained was 26.7 ±1.7
              Ib/ft3.

-------
The test material was not fed into the blast or the reverberatory furnace again until  later in the  afternoon.
At that time, the test feed was introduced at an 11 percent weight ratio into blast furnaces #1 and #2 and
reverberatory  furnace  #1. The test material was fed  to both blast  furnaces to ensure that both  furnaces
would contain  the same material at the start pf the third day of the experiment.  During the  third  day,  Exide
planned to use blast furnace #1 for processing of test materials.

Day Three

The test material feed  ratio in Blast Furnace #1 was increased to 13 percent and Blast Furnace #2 was
fed regular feed to serve as the control. The test material was pre-mixed with the regular feed prior to
charging the furnaces to eliminate layering of test materials within the furnaces.  Exide decided to reduce
coke input to the blast furnaces  because the  test material was serving as a supplemental source of carbon.
The reverberatory furnace remained at a feed ratio of 11 percent of the test material. Again,  material
accumulated  in the reverberatory furnace throughout the day.

Day Four

The reverberatory furnace showed  continued signs of material buildup, crusting and  sluggish performance.
Exide decided not to feed test material to the  reverberatory furnaces until the  next day. The blast furnace
test feed  ratio was held constant at 13 percent test material.

Day Five

Beginning at 8:00 AM on the final day of the test, the  reverberatory  furnace was fed at a ratio of 7 percent
test material.  No crust accumulation in  the  reverberatory furnace was noted.  However, the reverberatory
furnace still performed sluggishly.  Exide plant  management  hypothesized that the  sluggish performance
was attributed to the slow rate of burning associated with the relatively large pieces of matenal in the test
feed. They concluded that it was  not viable  to process  Tonolli site  materials in the reverberatory furnaces
without size reduction of the battery case materials.

Both blast furnaces  were fed test material at 20 percent by weight  until the operation of one of the furnaces
was discontinued in order to complete scheduled  repairs  and maintenance.  The testing  was continued
using the second blast furnace  and the  overall evaluation was concluded by 10:00 PM on September 13,
1991  when all the Tonolli  material  had been processed.
                                                 31

-------
                             2.0  RESULTS AND  DISCUSSION


In order to assess the viability and economics of the process,  CHMR/Exide recorded the settings of various
plant parameters, the production figures  for both sets  of furnaces, and stack parameters.  In addition
CHMR obtained samples  of the input material slag and lead.  The sampling was conducted in  accordance
with  the QAPP. The  results from the sampling  and analysis are presented and discussed below.

All statistical analyses were conducted according to the procedures outlined in  Section 5 of the QAPP. All
confidence ranges,  q-tests, analyses of variance (ANOVA analyses), etc. were performed based on 90
percent confidence limits.

In-depth analyses were performed  only on the  blast furnace  data. No statistical analyses were conducted
on reverberatory furnace parameters, because  the experienced furnace operators  had already determined
that the reverberatory furnaces  could not accept the battery  case  material feed as received from the Tonolli
site.

2.1     TEST  MATERIALS

The  test materials consisted of pieces of rubber and polypropylene, typically  shredded to approximately 1
to 3  inches in  size, combined with reddish-brown sludge,  dust, bits of concrete and iron, small wood scraps
and  pieces of cloth. Because of the varying  particle sizes  and shapes, the material was not densely
packed.

The  test materials were  sampled for various parameters,  including  density, lead content, sulfur content,
TCLP  values,  percentage rubber, and  other parameters. The results from these  analyses  are presented
in Table A-1,  which  shows lead concentrations ranging  between 0.28 percent and 15.7 percent, with  an
average of 3.5 percent.

The  wide range in analytical results  from analyses of the Tonolli  material was attributed to non-homogeneity
in the material, rather than errors in the analyses. CHMR reviewed  the  analytical procedure  and QA/QC
notes  for the  analyses, and determined that no obvious  errors in analyses existed.  Analyses  1 through 4
were of samples comppsites  of the material on the trucks  loaded  from the  site (composited from four
different grabs of material taken from the trucks). Analyses 5 and 6 were each  composites  of material
obtained from five different locations in the pile  of material  present at the smelter.  Analyses 7 and 8 were
duplicate analyses of material from one location in the pile. The  composites for analyses 5 and 6 included
one  grab which contained large amounts of reddish brown sludge. This sludge  apparently contained a very
high fraction lead. Thus, by averaging all  the analytical  results, CHMR obtained  an average which was
representative  of  approximately 30 grab samples taken  of the material. Based on this,  CHMR concluded
that  much  of the Tonolli material contained relatively low concentrations of lead, with scattered higher
concentrations, and an average concentration  of  3.5%.

2.2     FURNACE  INPUT  PARAMETERS

The  input parameters  recorded included air flows, oxygen consumption, back pressure, and  a  record of
materials introduced  into the furnaces. These  parameters were  recorded by  Exide  and CHMR personnel
during each shift. Table A-2 presents a summary of effects of the test material on the various parameters.

2.2.1  Blast  Air

Air enriched with oxygen is used in the blast furnace to oxidize  coke and other combustible material to
maintain a  sufficiently high temperature to  melt and fuse the  material in  the furnace. The air is enriched
with  oxygen to produce higher  flame temperatures, more efficient burning, and as a side benefit, smaller
bjowers are required to introduce extra oxygen than are required to  move the  required  larger volumes of
air. The required rates of air and oxygen inputs to the furnaces are  determined by the operators and set
manually. The air and  oxygen settings are  recorded at the  beginning  of each shift, and whenever they are
changed.
                                                32

-------
                                           TABLE A-2
                 SUMMARY OF EFFECTS ON BLAST FURNACE  PERFORMANCE
Parameter
Air
Oxygen
Back Pressure
SO2 Emissions
Lead Production
Slag Production
Lead Concentration in Slag
Lead Concentration in Slag
Sulfur in slag
Antimony in Slag
Silica in Slag
FeO in Slag
Effect of Adding Test Feed
to Furnace
Increase on furnace #2
No observed difference
Increased
No observed difference
No observed difference
No observed difference
Increased from 2.2 to 3.7%
Reducing environment
No observed difference
No observed difference
No observed difference
No observed difference
Probable Cause
Probably due to build-up;
otherwise insignifcant

Partially due to over-coking



Over-coking
Too much carbon




Response
Small problem no
response is necessary

Decrease particle size



Reduce coke input
Reduce coke input;
increase iron input




The relative air consumptipn in Blast Furnace #2 while regular feed only was processed was 6.75±0.25,
and while the Tonolli material was processed was  7.42±0.12. The  difference in  air consumption in Furnace
#2  between times when test feed was processed  and when it  was not appears to be largely due to a
significantly decreased air consumption rate  on Wednesday,  September 11, which occurred when  no test
feed was processed in the furnace.  It also correlates to a time when the overall production rate of the
furnace  decreased, possibly due to attempts by the  operators to  reduce coke buildup in the furnace.  This
buildup  was only  partly attributable to the test feed.

2.2.2 Back Pressure

The furnace back pressure is a measure of the pressure against  which the  air blowers must push in order
to force air into the furnace. The back pressure increases as the air required  by the furnace increases.
At constant air, the back  pressure is a measure of the resistance of the material  inside the furnace to the
flow of air. The back pressure increases when small particles are fed to the furnace or if material begins
to back up inside the furnace.

The use of test feed  caused  an increase in back pressure in  the  blast furnace. The average back pressure
while regular feed was  processed was 4.95+0.6 inches of water, and 7.42+0.4inches of water when test
feed was charged to the furnace.

Although some of the apparent correlation between back pressure and test feed input may be attributable
to buildups within the furnace caused by over-coking, the evidence is strong  that the Tonolli  material
significantly contributed to the back pressure increase. The most likely reason  for  the increase in back
pressure while processing Tonolli material  is that the Tonolli material was large enough that it burned
relatively slowly,  but  sufficiently small to fill some of the pore spaces inside the furnace feed shaft.

The increase in  back pressure seen during the  evaluation probably had  little affect on overall furnace
performance or overall process  economics.  However, as the  back  pressure increased, the blowers had
to work  harder to  blow air into the furnace, and at higher back pressures  (above 30 or 40 inches of water),
the blowers will stall. Therefore,  based on the data, which suggest a 5  inch back pressure increase per
10  percent addition of battery case material, the  maximum sustainable battery  case  material  feed ratio is
between 30 percent  and  50  percent by weight.
                                               33

-------
2.3       FURNACE  OUTPUT  PARAMETERS

CHMR monitored the  output of parameters such  as sulfur (in the form of S02 and calcium sulfate sludge)
lead,  and slag.

2.3.1  Sulfur

The Tonolli material was found to contain 2.6±1.0 percent sulfur.   Overall, this concentration did not
represent a significant difference with regular feed material, which may contain 2 percent to 5 percent
sulfur. Therefore,  no significant differences in overall plant  sulfur emissions  were anticipated. However,
CHMR/Exide monitored the fate of sulfur in the process to ensure that processing the test material did not
result in an increase in production of calcium sulfate sludge,  S02  emissions, or sulfur concentration in the
slag.

Approximately 50 percent of the sulfur entering a blast furnace leaves as oxides in the flue gas stream.
Nearly 100 percent  of this sulfur at Exide's Reading smelter is removed as calcium sulfate sludge from the
S02 scrubber system. However, a small portion of the sulfur  in the flue gas is  released as stack emissions.
Therefore,  CHMR/Exide monitored  both the calcium sulfate  sludge generation and SC^  concentrations in
the stack emissions.

SOo  Emissions
CHMR monitored both stacks at the smelter. Each stack system is connected  to the corresponding blast
and  reverberatory furnace. The average sulfur stack emission in system #1 was 64±6 ppm, while the
average stack emission  in system #2 was 69±9 ppm. Both of these values were below Exide's  permitted
average of approximately 110 ppm.  No statistically significant differences exist  between the emissions from
the two systems. The overall average plant SO, concentration was  66±6 ppm.

ANOVA analyses indicate no differences were demonstrated between S02 emissions when the test material
was  being processed, and when it was not  being processed, for either set of furnaces. In addition, there
is  no significant  correlation between  SO, concentrations as a function of test material input ratio. Therefore,
CHMR/Exide conclude that the Tonlti  feed material did not have a  significant affect on the SO2
concentration in  the  stacks.

Calcium  Sulfate Sludge  Production

During each shift, specific gravity measurements of slurry generated  from the air emission control
equipment (scrubbers) were taken by the operator on duty. The specific gravity is related to the calcium
sulfate concentration in the slurry,  and therefore gives a measure of total sulfur uptake in the sludge.
Typical slurry specific gravity is between  1 .1 and 1 .3. Slurry specific  gravities for both air emission control
systems  averaged 1.18±0.02, and showed  no correlation with test feed input.

At the end of each shift, the amount of slurry was calculated by counting the number of 10 cubic yard
tankers transported from the scrubbers to the on-site sludge  dewatering  facility. The number  of tankers
varied only between 2 and 4 per shift, with a total of 9 trucks per day except Thursday, September 12,
when 8 trucks were transported. Normally, between 8 and 10 tankers per  day  are transported.  Therefore,
CHMR/Exide conclude that there was no significant increase in calcium sulfate sludge production due to
processing the  Tonolli material in the blast furnaces.

2.3.2    Slag  and Lead  Production  and  Quality

The  amount of slag  and lead produced  by  the blast  furnaces were critical experimental parameters. The
amount and quality of lead produced is important for  obvious reasons, as  lead is the salable product from
smelter operations. The  slag generation rate was also important, as  slag disposal represents a significant
operating  expense. The  lead concentration in the slag is also  important because it represents a  potential
loss of salable lead  product.

Lead and  slag production for each  furnace  during  each shift were  measured.  ANOVA statistical  analyses
were performed to determine if significant differences existed between the amounts  of slag or lead
produced while  the test materials were run versus the amounts  produced while  only regular feed was
processed in the furnaces. The tests indicated  no statistically significant  change in lead or slag  production
                                                34

-------
rates while the test feeds were run in either furnace. The only significant drop in production during the
week occurred in Furnace #2 on September 10,  when  lead production dropped due to  over-coking.

Lead samples from the blast furnaces were obtained during each shift. The samples were analyzed by
Exide personnel using Spectrometer Lab Test 201 equipment to determine concentrations of trace metals
in the lead. The results from the lead analyses indicated  no significant increase in contaminants in the lead
product.

Composite samples of slag were taken as the slag was being tapped from the furnaces. The molten slag
samples were collected  by the  Exide operators by inserting  a  shovel into the furnaces in accordance with
the QAPP. Table A-3 shows the results of the analyses of slag samples taken from the furnaces when they
were fed regular feed , and regular feed and test feed mixed  (with the test feed ratios noted). The table
shows  no consistent differences in sulfur, silica, antimony, and iron oxide concentrations when the test feed
was processed  in the furnaces. The results do show a  significant difference in lead concentrations in the
slag. When only regular feed was  processed, the lead  concentration was 2.21+0.6  percent.  When  Tonoiii
material was  added^ the lead  concentration increased  to  3.7+0.7 percent.

Much of this  difference  may  be attributable to the  problems  encountered when both furnaces were over-
coked earlier  in the week. The over-coking problem was intensified by the addition of test feed.  High coke
increases the concentration of lead in the slag.  On Wednesday, September 11,  the  plant responded by
reducing  the amount of coke and increasing the iron  fed to the furnace to maintain a reducing environment
with less coke.  The data show  a decrease  in the lead  content in the slag beginning during the third shift
on September 11 (samples  13 and  14) and continuing throughout the remainder of the week. By
September 12 and 13 (samples 15 and 16), the lead concentration in the slag  was reduced,  and a relatively
stable slag composition was maintained at 2.5 percent, which is approximately equal to the lead
concentration  in  slag when no Tonolli  input was  fed to  the  furnace.
                                                35

-------
                 TABLE A-3
       BLAST SLAG ANALYTICAL RESULTS

             REGULAR FEED ONLY
Sample
1
2
3
4
5
6
7
AVERAGE
Lead (%)
2.8
3.1
1.1
2.7
1.9
2.5
1.0
2.2±0.6
Sulfur (%)
3.0
3.9
5.2
3.0
4.9
5.0
2.9
4.0+0.8
Si02 (%)
24.8
29.5
15.1
24.4
21.7
4.7
23.9
23+3.4
FeO (%)
30
32
63
36
46
30
43
40+8.6
Antimony (%)
1.5
0.1
—
0.5
0.5
1.0
-
0.72+.0.5
     REGULAR FEED AND TEST FEED MIXED
(% test feed in parentheses next to sample number)
Sample
8 (7%)
9 (7%)
10 (11%)
11 (11%)
12 (13%)
13 (13%)
14 (13%)
15 (13%)
16 (20%)
Average
Lead (%)
3.3
5.3
4.8
2.6
3.3
4.7
4.5
2.5
2.5
3.7 + 0.7
Sulfur(%)
1.4
3.6
5.9
2.1
1.2
4.5
5.2
1.8
3.2
3.2+1.0
SiO2 (%)
33.9
30.0
21.4
32.6
32.6
21.2
2.36
28.0
18.8
27+3.7
FeO (%)
29
24
47
33
30
44
42
48
55
39±6
Antimony (%)
0.3
0.2
2.2
0.6
0.2
0.4
0.4
0.4
0.2
0.5+0.4
 All confidence intervals based on 90%  confidence level.
                     36

-------
             APPENDIX B
 RECLAMATION OF LEAD FROM THE NL
    INDUSTRIES SUPERFUND SITE IN
          PEDRICKTOWN,  PA


Description of Evaluation and Results and Discussion
             November, 1993
                  37

-------
                                     1.0   INTRODUCTION


The  Center for Hazardous Materials Research  (CHMR) and  Exide  Corporation (Exide)  performed a joint
research study to determine the feasibility and economics of  using secondary lead smelters for the
recovery of lead  from leadcontaining  materials. Under the  project CHMR/Exide conducted an
evaluation to determine the feasibility and economics of reclaiming lead from the NL Industries, Inc.
Superfund site  in  Pedricktown,  NJ.  This evaluation  was conducted  in two  stages: a preliminary
investigation and  a larger-scale evaluation.

As part of the preliminary investigation, a total of 19 trucks with 20 to 40 cubic yard  capacities were
loaded with lead-containing material on January 29 and 30, 1992. The trucks represented different
types of material  found on the  Pedricktown site with lead  contents ranging  between 36  and 65 percent.
A total  of 372 tons  of material were processed  during this  initial investgatton. Information  gathered
from the preliminary  test assisted  CHMR/Exide  in determining the feed  rates and types of material to  be
processed through the secondary  lead smelter.

The  purpose of the preliminary study was to process the  different types of material through the furnaces
and  determine the initial  response  of the furnaces to the material. This provided CHMR/Exide with the
information necessary to complete the  next  stage of the evaluation, which  consisted of processing the
material over a longer time through the secondary lead smelter.

After receiving  permission  from the EPA Project  Officer and  the  EPA Remedial Project Manager (RPM),
the  second  stage  of the investigation  was initiated.  Materials were excavated,  loaded,  and transported
to  Exide's secondary smelter in Reading,  PA. The  material was weighed and stored in an  area  isolated
from other  feed material  prior to beginning the  evaluation. During the second evaluation, which
occurred over three months, approximately 1200  tons  (2.4 million pounds)  of Pedricktown material were
processed.
                                                38

-------
                           2.0  DESCRIPTION  OF   EVALUATION


The purpose  of the evaluation was  to determine the feasibility and economics of processing the
material from the NL Industries,  Inc.  Superfund site using secondary lead smelting  technology. The
initial  step was a preliminary test during which  19 truckloads were processed. This was followed by a
larger-scale  investigation  that spanned three months.

2.1 RECLAMATION  PROCESS

The reclamation of lead  from Superfund and other lead-containing  materials  is  based on existing  lead
smelting procedures and basic pyrometallurgy. The materials are first excavated from Superfund sites
or collected from other sources.  Then they are preprocessed to reduce particle size, and to remove
rocks, soil, and other debris. The materials are then transported to the smelter.

At the smelter, the  materials are fed  either to  the  reverberatory or blast furnaces, depending on  particle
size or lead content. The two reverberatory furnaces normally treat  lead from waste lead-acid batteries
as well as other  lead-containing  material.  The  furnaces are periodically  tapped to remove slag, which
contains 60 to 70 percent lead, and a soft, pure  lead product. The two  blast  furnaces treat the slag
generated from the  reverberatory furnaces, as  well as larger sized  leadcontaining waste.  These
furnaces are  tapped  continuously for lead,  and  intermittently to  remove the slag, which  is transported
off-site for disposal. The reverberatory and blast  furnace combination at  Exide  can reclaim  lead from
batteries and waste with greater  than 99  percent  efficiency.

2.2     SMELTING  PROCESS  DESCRIPTION

Exide's Reading,  PA, secondary  smelter is primarily engaged in the reclamation of lead from spent
lead-acid batteries and other  lead-containing materials. Exide reclaims  lead  using bpth reverberatory
and blast  furnaces. The  plant operations  are typical of the secondary lead smelting  industry.

2.3     EXPERIMENTAL DESIGN

The material  obtained  from  the  Pedricktown site  varied in  size,  lead  content, and overall texture and
structure. These factors determined the method  of processing  through  the secondary lead smelter.
The majority  was processed through  the  reverberatory furnaces, while the blast furnaces were used for
larger  pieces of material, such as lead hard heads (large  chunks of metallic  lead) and ingots found at
the site.

Approximately 372 tons of  material  were  processed during the preliminary  investigation.  Since the
objective of the  preliminary investgation was to  study the effects of the  Pedricktown  material on furnace
performance, this stage of  the evaluation  featured the  most diverse variety of material.

During the large-scale evaluation,  CHMR/Exide processed approximately 1200 tons of material. The
majority of material was  processed  through the reverberatory furnaces over a two mpnth period.   During
the third month,  the  material had to be processed through the  blast  furnaces due to its size and
composition.

2.4     EXPERIMENTAL FEED

Tables B-1 through  B-4  provide  the results of detailed analyses of the  NL  Industries site  material during
the preliminary and large-scale investigations. Table  B-1  shows the results of analyses of samples
taken  during a preliminary field reconnaissance to the site during December 1991. The parameters
analyzed  included  lead, antimony,  calcium, silicates, sulfur, arsenic,  tin  and  iron were analyzed mainly
to determine the metallurgical aspects of the  feed and its suitability  in the smelting process.  Further
analyses were conducted of the  material  which was fed to the  furnaces during  January 1992. The
analytical  results are presented  in Table B-2. Composite samples of the material were taken as it
arrived in trucks at the smelter. Analyses  of lead and silica were conducted  to provide baseline
metallurgical data for the  materials.  Fluorine  and  chlorine were analyzed  to quantitatively demonstrate


                                                 39

-------
that the material contained negligible  quantities of these elements,  and no halogenated compounds.
Aluminum was analyzed because there was  a concern among plant management that the material may
contain  some  aluminum, which is prohibited in the furnaces,  and sodium was analyzed for because it
represented a  potential impurity in  the lead  products.  In general, the results showed no major areas of
concern for the material to  be fed  to  the smelter, and a feedstock which contained over  50% lead.

Table B-3 shows the results of analyses conducted  on composite samples taken of the material sent to
the smetter during  the  longer term evaluations, August through October 1992.  The analyses included
moisture analyses  for the August  and September material,  because  moisture  levels appeared to  be a
potential concern to furnace  operators. The  results showed that the  levels were  not  pf concern. The
material shipped  during  October  which  was fed to the blast furnace,  appeared to  be similar to
reverberatory slag and was composed primarily of lead and iron  One load  of wooden pallet material
was analyzed  for Btu content, since  it was anticipated to burn in the  furnaces.

2.5     CHRONOLOGY OF THE  EVALUATION

The  following  provides the schedule and different methods used for processing the material during  the
preliminary  and large-scale investigation.

2.5.1    Preliminary Test - January 1992

Nineteen trucks brought  a wide variety of the debris  from the site to the smelter at  Exide   Initially,  test
material was fed directly into  the reverberatory furnaces as 100 percent of the total feed. This  caused
various  malfunctions in  the furnace, including  build-ups in the furnace  and  breakdowns  of the belt feed
system.  The  material was successfully fed at a 50  percent weight ratio into the reverberatory furnaces.
No material was fed to the  blast furnaces.

2.5.2 Large-Scale Test - August through October 1992

The larg e-scal e investigation took place through the three months that were  used to  process the
materi al. During the first two months, the  material consisted primarily  of dross,  slag, and debris, which
was  processed mainly through the  reverberatory furnaces. The  material during  the third month
consisted  of large pieces of slag, which was  processed through the blast furnaces  at the smelter. The
slag  also  featured  a lower concentration of lead than  the  previous material. The following paragraphs
provide  a  short summary of the materials, and the methods used for processing the material.

2.5.2.1  August

The  initial  19  trucks for  the large-scale investigation transported various types of dross material, which
were  mixed with regular feed  at a 40 percent (by weight) ratio and fed into  the  reverberatory furnace.
The  larger sized  material was sorted  out and processed through  the  blast  furnaces. These  operations
continued  until the initial truckloads of material had been depleted. The average  lead concentration of
the dross material was 48 percent.
                                                40

-------





















i
3
I






























1

*ST

< £
H O
ei|i
ELD SAMPLE
PRIES (PEDRM
DECEMBER 1
C w
Q
Z
_J
Z












y__

-p c
.c *
S 1^
c n.
"c
0
H
11
*- H,
!», ©
3 P
™ 1U
«s *?
12
 B

E s?
- o I
(BJ C5 0
1 ||
e < •— :
o

S *"**
S T, §
— re o
| Jl







Sample Type/Notes










>5
o
T™

O
T™
O
<4«*
IT"

sf
S
o
2
V*
O


55

o
(0






r*
i
Dross from Pedricktov
o
»r~








>5
CO
o








CM
o




S«

o
«o








Duplicate of Sample A














se
CM




6s
O
*••
T™
O
S
o


j5
w
o
10

0
S3
in
Ji
o.
jS
to
1
I
g
«f
w
e
t3
00
00














g
^-*




5?
5
*~
es
o
o
4~*
•r-


S^
GO
(O








S
Q


co

o

5?
T-
C3













T-



gS

ft
a
«T"

I
CM
IB
W
S
13
S8
(O
r-
o
cs
c*> o
CM CM
0 O

# f
T- O
o o





s« a?
CN CO
CO CD
W «M




CO
o
CM 5r
T- e»



mJ9 ~*JS p^Jffil «Jp i^B ij^ffl A^M »,«i
f"i ^3T *•"• •** "*™* OO iW f'if
10 liO 0) 0) (0 t"M 10 fs«f
(0 O 10 (0 O M^

P S
«5 W
til %
*~ OL
S s?
0 $
a ,« .«
£ ^ I 1 - c
1 1 1 1 1 I
3 IS 55 S? "» -0
tj » a ? ,g Is §
S 1 1 1 1 i I I
«,y"X3t3°* s^Q
Sas?^ g'll-o
•-^rjtb— IB 0 o
D Q >-~ oo t/) 03 _1 CC






ss
fO
O

sP
5s-
O
^™
O
B«
^





^
c>



-9, «»5 »5 ^ sj
n T- tn J_ J_
SJ; 3 § 5 g








Lead debris
Soft lead dross
Orange/yellow Dross
Black Dross
AVERAGES;














0

Q.
E
m
ff)
"5
X

















41

-------
                                                           TABLE B-2
                                       FEED STREAM ANALYSES NL INDUSTRIES EVALUATION
                                            PRELIMINARY  EXPERIMENT JANUARY 1992

                                   Quantity Concentration
Sample Type/Notes
LEAD DEBRIS
LEAD DROSS
LEAD SLAG
SLAG AND DEBRIS
SLAG AND DEBRIS
SOFT LEAD DROSS
LEAD SULFATE
SLAG AND DEBRIS
LEAD HARD HEAD MATERIAL
BATTERY CASING AND DEBRIS
MATERIAL FROM INSIDE BLDG
SLAG AND DEBRIS
COMPOSITE OF TWO PILES AT SITE
SLAG AND DEBRIS (incl. B2 P3&4)
SLAG AND DEBRIS
TOTAL
Processed Lead
(Ibs) (percent)
40,530
87,310
18,280
42,620
81,740
44,210
30,050
34,950
40,460
32,680
77,040
43,070
45,100
84,360
42,070
744,470 Ibs
57%
61%
54%
61%'
61%
54%
59%
65%
36%
53%
55%
65%
63%
59%
61%

Flouride
(percent)
<0.0001
<0.0001
<0.0001
<0.0001
<0.0001
<0.0001
<0.0001
<0.0001
<0.0001
<0.0001
NA
<0.0001
NA
<0.0001
<0.0001

Chloride
(percent)
0.51 %
0.06%
0.12%
0.11%
0.04%
0.08%
0.06%
0.14%
0.04%
0.08%
NA
0.14%
NA
0.24%
0.11%

Silicates
(percent)
6.9%
3.1%
3.5%
3.4%
1 .5%
1 .6%
7.9%
2.4%
5.5%
4.7%
4.2%
2.4%
3.3%
3.63%
3.4%

Aluminum Sodium Other analyses
(percent) (percentages)
0.55%
0.16%
0.18%
0.41%
0.22%
0.26%
0.12%
0.22%
0.40%
0.85%
NA
0.22%
NA
0.34%
0.41 %

1.35%
0.38%
0.28%
0.59%
0.62%
0.52%
0.12%
0.16%
0.65%
0.13%
NA S: 3.3 CA:0.9 Sb: 0.6%
0.16%
NA S: 2.7 Ca: 0.3 Sb: 0.8%
0.68%
0.19%

Weighted  Average:
58%   0.00%    0.13%    3.59%   032%
0.4S%

-------
                                              TABLE B-3
                      FEED STREAM ANALYSES NL INDUSTRIES  EVALUATION
                                      AUGUST -  OCTOBER 1992
                         Quantity
                         Processed
          Sample Type/Notes   (Ibs)
Metal   Concentration
Lead      Moisture   Antimony
(percent)   (percent)   (percent)
    Silicates   Sulfur    Iron (FeO)  Other
    (percent)  (percent)  (percent)    analyses (%)
AUGUST MATERIAL
Lead Dross & debris
Lead Dross & debris
Lead Dross & debris
Slag & debris
Slag & debris

133,779
112,656
105,615
182,470
262,700

43%
55%
54%
44%
47%

9.8%
10.4%
9.1%
12.6%
8.7%

0.8%
NA
NA
0.6%
3.4%

5.7%
3.4%
7.9%
4.2%
3.7%

2.7%
NA
NA
3.0%
0.9%

9.6%
NA
NA
1 .4%
4.6%





Ca 0.53%
          SEPTEMBER MATERIAL
          Lead debris           486,630       57%
          Black dross           138,140      51%
          Iron cans             13,230      <1%
          Battery Cases Sdebri    60,250      44%
          Pallets               39,810      7%
          Baghouse bags         49,000       69%

          OCTOBER MATERIAL
          Wooden pallets from I    10,300     6.5%
          Slag                600,900       32%
          Slag & debris         261,820       28%

          Total Processed:     2,457,300 Ibs
          Weighted avg. composition:      43.1%
            13.4%
            11.7%
              NA
             9.6%
              NA
              NA
              NA
              NA
              NA
           11.3%
 NA
2.3%
 NA
 NA
 NA
 NA
 NA
 NA
 NA
                       2.0%
NA
NA
NA
NA
NA
NA
NA
NA
NA
                                4.7%
2.1%
0.8%
 NA
1.0%
 NA
 NA
 NA
 NA
 NA
 4.0%
   NA
> 80% Iron feed
 5.1%
   NA
   NA
  NA Btu/lb: 4945
 2.6%
21.7% Ca: 0.14%
                                                 8.5%
2.5.2.2  September
 In September, a total of 19 truckloads containing various types of lead  debris were  processed through the
 smelter's reverberatory  furnace. The material varied in overall weight  and density,  with  an average lead
 concentration of 53  percent.  In addition, the material had relatively high amounts of calcium and therefore
 needed to be processed through the reverberatory  furnaces at tower feed rates (20 to 30  percent of typical
 feed,  by weight) than the material  processed  during the previous month. An  excess  of calcium  in the
 reverberatory furnaces  causes  build-ups inside the  furnaces.
 2.5.2.3  October
 CHMR/Exide  performed the final stage  of the large-scale investigation  in  October.  The  material consisted
 primarily of slag  and debris, which  was larger in size than  previous material,  and therefore needed to be
 processed through  the blast furnaces. This slag and debris material contained lead concentrations of
 approximately  30 percent. The final 20 truckloads of the Pedricktown material were processed by early
 November  1992.
                                                   43

-------
                            3.0  RESULTS AND DISCUSSION


In order to assess the viability and economics of the process, CHMR/Exide obtained production sheets,
samples, sample results and other  general information of furnace performance to evaluate the processing
of the material. All  statistical analyses were conducted according to the procedures  outlined in Section 5
of the Quality Assurance Project Plan for the project. Analysis of variance (ANOVA)  was performed on the
data sets.  The ANOVA compares  two experimental means to determine if a significant difference exists
between  them. The null hypothesis is that no  difference exists between the data set. The governing
equations  are as follows:
                                          Z=ts
                                              and
where s is the standard deviation across all data, n is the number of samples analyzed, f is from statistical
tables (based on 90 percent probability level), and x is the calculated mean. When Z > D, the null
hypothesis is not rejected, and no significant difference between the means has been demonstrated. On
the other hand, when D > Z, then a significant difference does exist. The q-test, which rejects outlying
data, was also performed on each data set as required prior to the ANOVA.

3.1     TEST MATERIAL

The Pedricktown material was analyzed for percent  moisture, silica, antimony,  iron oxide, lead, sulfur, and
calcium. Table B-4 presents a summary of the analytical results of the  material processed over the entire
investigation.  The January material  was not analyzed  for all of these parameters, and  the October slag
and debris material  was only analyzed for total weight  percent of lead.

3.2     SUMMARY  OF PRELIMINARY INVESTIGATION  RESULTS

CHMR/Exide conducted the  preliminary investigation  in which material was processed through the smelter
between January 29 and February 2,1992.  During this  preliminary  investigation,  CHMR/Exide  processed
approximately 372 tons of material  containing between 36 and 65 percent  lead. The results from the
preliminary  investigation showed that the material could  be processed through the reverberatory furnaces
at feed rates of up to a maximum of 50 percent by weight test material. Higher  feed rates caused build-ups
and break-downs in the furnace feed system  due to the weight of the test material,  which was heavier than
the typical  Exide feed.

3.2.1   Lead and Slag Production and Quality

The amount and nature  of the lead and slag produced  by the reverberatory furnaces when  processing the
test material were critical experimental  parameters, since the lead is the salable product from  the smelter,
and the reverberatory slag is a feed to  the blast furnaces.

Blast furnace lead  and slag production  were not monitored  during  the  preliminary experiment,  because
the test feed material was fed exclusively to the  reverberatory furnaces.
                                               44

-------
                                            TABLE
                    NL INDUSTRIES FEED MATERIAL - SUMMARY ANALYSIS
FULL-SCALE TEST
PARAMETER
% MOISTURE
% SiO2
% ANTIMONY
% FeO
% LEAD (AVG)
% LEAD (RANGE)
# OF FEED PILES
% SULFUR
JANUARY AUGUST SEPT
MATERIAL MATERIAL MATERIAL
N/A 10.1%
3.6%
N/A
N/A
56%
36 to 65
15
3%
5.0%
1.0%
3.1%
46%
42 to 52
3
1.3%
8.7%
N/A
2.3%
4.6%
52%
7 to 69
6
1.3%
OCT
MATERIAL
N/A
H/*
N/A
N/A
31%
6.5 to 31
1
N/A
3.2.2  Reverberatory  Furnace Lead Production and  Quality

The quality of the lead  produced by the reverberatory  furnaces  during the January test  was determined
through the use of Spectrometer Lab Test 100 analysis on-site, which measures the concentration of trace
metals in the lead product.   CHMR/Exide  representatives collected 20 lead samples from the test
reverberatory furnace, and 10 lead samples  from  the  control reverberatory furnace. The average  results
of these samples can be seen  in Table B-5, which shows a comparison of the  lead produced  during
processing  of the test material and the  lead from the control reverberatory furnace processing typical feed.
the  values given for the metals  are relative units. The  table shows that the quality of the lead produced
by the test reverberatory  furnace is  comparable with typical reverberatory lead. All of the experimental
means are statistically equivalent at a 90 percent probabi ity level  except for that of antimony:  0.249+0.0028
units of antimony when test material was fed versus 0.041+0.008 when only regular feed was fed. This
was anticipated, because the test material was known to contain relativefy high concentrations of antimony.

Total lead production in  the test  and control reverberatory furnaces remained roughly equivalent during the
evaluation,  with perhaps a slightly significant increase in production for the furnace fed test feed. The effect
of the material on total furnace production was more precisely quantified during the longer term evaluation.

3.2.3   Reverberatory Slag Production and Quality

CHMR obtained samples of the reverberatory  furnace slag for both the test and  control furnaces. The slag
was analyzed  for total lead,  antimony, silicates,  sulfur, and iron. The results from the analyses  are
presented in Table B-6.  The results showed a significant decrease in lead concentration in the slag - from
an average of 73% in the control furnace to 48% in the test furnace. At the same time, the concentration
of silicates and iron increased in the slag from the furnace fed test feed.

Total slag production for the furnaces was only  cursorily reviewed, since it was better quantified during the
longer term evaluation.   It seemed to decrease slightly during the evaluation, although the decrease was
only barely statistically  significant.

The combination of a decrease in lead  concentration with  a potential decrease in slag production  indicates
a significant decrease in the  amount of lead  flowing from the reverberatory furnace  to the blast furnace.
At the same  time, lead  production in the reverberatory  furnace increased,  Indicating that at  least some  of
the lead input was effectively shifted from the slag to lead product in the reverberatory furnace.

-------
TABLE B-5 REVERBERATORY LEAD FROM TEST MATERIAL VERSUS TYPICAL FEED LEAD
                FOR JANUARY,  1992 PRELIMINARY INVESTIGATION

            REVERBERATORY LEAD FROM TEST MATERIAL (TEST FURNACE)

AVQ LEAD FROM TEST MATERIAL (x):
STANDARD DEVIATION (S):
NUMBER OF SAMPLES (n):
TRUE MEAN (M):
Pb
13,812
483
20
13812
±
186
Sb
0.249
0.073
20
0.249
±
0.028
Sn
0.000
o.ooo
20
0
As
0.000
0.000
20
0
Cu
0.037
0.004
20
0.037
±
0.002
Ni
0.012
0.008
20
0.012
±
0.004
Bi
0.012
0.003
20
0.012
±
0.001
Ag
0.003
0.001
20
0.003
±
0.000
Fe
0.000
0.000
20
0
Te
0.004
0.001
20
0.004
+
0.000
Zn
0.000
0.000
20
0
         TRUEMEANp-x±
 St
V7T
VALUE FOR t BASED ON 90% PROBABILITY LEVEL
       REVERBERATORY LEAD FROM TYPICAL FEED MATERIAL (CONTROL FURNACE)

AVQ LEAD FROM TYPICAL FEED (x):
STANDARD DEVIATION (S):
NUMBER OF SAMPLES (n):
TRUE MEAN (M):
Pb
13317
779
10
13317
±
446
Sb
0.041
0.014
10
0.041
±
0.008
Sn
0.000
0.000
10
0
As
0.000
0.000
10
0
Cu
0.040
0.006
10
0.040
±
0.004
NI
0.020
0.006
10
0.020
±
0.004
Bi
0.012
0.003
10
0.012
±
0.002
Ag
0.004
0.001
10
0.004
±
0.001
Fe
0.000
0.000
10
0
Te
0.004
0.000
10
O.OO4
±
0.000
Zn
0.000
0.000
10
0
         TRUE MEAN p - x ±
 St
77T
VALUE FOR t BASED ON 90% PROBABILITY LEVEL

-------
                                TABLE B-6
               REVERBERATORY  FURNACE SLAG COMPOSITION
        DURING TEST WITH NL INDUSTRIES MATERIAL - - January 1992

                       Concentration
                       Lead      Antimony Silicates      Sulfur     Fe
Date Sampled	(percent) (percent)  (percent)     (percent)   as % FeO
TEST FURNACE
  29-Jan-92

  29-Jan-92
  29-Jan-92

  29-Jan-92
  29-Jan-92
  30-Jan-92
  30-Jan-92
  30-Jan-92
  30-Jan-92
  31-Jan-92
  31-Jan-92
  31-Jan-92
  31-Jan-92

  01-Feb-92
  01-Feb-92
  01-Feb-92
  01-Feb-92
  02-Feb-92
  02-Feb-92
  02-Feb-92
  03-Feb-92

AVERAGE:
STD. DEV.

CONTROL FURNACE
  29-Jan-92                 71.9%     3.9%       6.4%               2.60%
  29-Jan-92                 76.9%      3.7%        4.7%               2.20%
  29-Jan-92                 44.3%      3.6%        2.6%               2.70%
  29-Jan-92                 79.4%      3.8%        3.7%               2.70%
  30-Jan-92                 86.5%      3.9%        3.4%               2.90%
                           71.6%      2.7%        1.8%      5.2%     0.5%
  31-Jan-92                 78.9%      3.4%        4.1%               2.30%
  31-Jan-92                 79.7%      3.6%        4.2%               2.80%
                           68.0%      3.3%        3.8%      2.9%     0.8%

AVERAGE:                  73.0%     3.5%       3.9%      4.0%     2.1%
STD. DEV.                    11%       0%          1%       1%       1%

                                    47
78.7%
58.3%
43.9%
49.7%
42.2%
49.7%
33.5%
54.0%
40.1%
43.7%
41.6%
47.1%
71.5%
47.8%
82.8%
57.4%
28.3%
30.2%
29.9%
34.3%
29.1%
20.2%
12.4%
25.9%
48.2%
17%
3.4%
4.2%
5.6%
6.8%
6.6%
5.4%
6.6%
4.4%
9.9%
11.4%
9.9%
7.3%
2.9%
6.0%
2.2%
2.0%
2.3%
3.2%
4.7%
3.8%
3.6%
3.2%
1.3%
4.0%
5.4%
3%
3.3%
5.8%
20.3%
15.3%
14.9%
11.3%
15.1%
9.5%
13.4%
9.3%
13.1%
12.1%
5.1%
14.5%
1.5%
3.8%
23.0%
21.1%
18.8%
17.6%
19.2%
22.8%
30.3%
21.5%
12.4%
7%
0.7%
4.4% 3.6%
10.6%
8.7%
2.2% 3.6%
10.4%
19.2%
12.9%
16.1%
17.3%
16.7%
12.0%
5.3%
11.5%
3.8%
0.3% 9.8%
19.4%
20.4%
21.3%
22.1%
25.4%
26.5%
26.7%
24.6%
2.3% 12.3%
2% 8%

-------
CO

z
13
HI


5
HI
to
z
o
CO
CO
LU
CM
O
CO
   200
   150
   100 	   |  i
    50
                                                                                                  70
                                        HOURS FROM START OF TEST

                           _»_ JEST FURNACE     —   CONTROL FURNACE



                            ANOVA ANALYSIS  OF  EMISSION DATA
VARIABLE (EXPANATION)
x1,x2 (AVERAGE DATA VALUES)
s1,s2 (STANDARD DEVIATIONS)
n1, n2 (NUMBER OF DATA)
t1, t2 (FOR 90% CONFIDENCE LIMIT)
s (STANDARD DEV. ACROSS ALL DATA)
Z = ts ((n1 + n2)/(n1 n2)) A .5
D = abs(x1 - x2)
Signif. difference iff D > Z:
Conclusion:
TEST
FURNACE
0.49
0.49
45
1.64
0.60
0.21
0.51
CONTROL
FURNACE
1.00
0.59
45
1.64

Significant difference
x2 - x1 = 0.51 ± 0.19 |
                 FIGURE B-1 Sulfur Dioxide  Emissions from the Test and Control
                                     Furnaces - January 1992


   these analyses were  not made available to CHMR, although reportedly the vast majority of slag samples
   were non-hazardous. The amount of blast slag produced is a far more important parameter, and if is
   discussed  below.

   3.3.2 Lead and Slag Production

   Figures B-2 through B-7 present the lead and slag production for the three months of the large-scale
   investigation. The data used to generate the figures was taken from Exide's daily productions sheets. All
   of the values In the figures are normalized so that the average production of the control furnace is 1. This
   was done to  protect  confidential Exide production information.
                                               48

-------
                               ANALYSIS OF VARIANCE (ANOVA)
TEST
VARIABLE (EXPLANATION) FURNACE
x1 , x2 (AVERAGE DATA VALUES)
s1,s2 (STANDARDDEVIATIONS)
n1, n2 (NUMBER OF DATA)
t1 , t2 (FOR 90% CONFIDENCE LIMIT)
(STANDARD DEV. ACROSS ALL DATA)
Z = ts ((n1 + n2)/(n1 n2)) A .5
D = abs(x1 - x2)
1.22
0.24
25
1.66
0.24
0.12
0.22
CONTROL
FURNACE
1 .00
0.18
20
1.71
-i
                        Signif. dfference  iff D > Z:
                                     Conclusion:
Significant  difference
x2  - x1 =  -0.22 ± 0.10
                AUGUST REVERBERATORY  SLAG PRODUCTION
3  2


£
                                                                        n	zo	n	tf-
                  j   i   •7   i   •10   ii   n  ran  n   ™   n
                                      DAYS PROCESSING*

                -TEST MATERIAL REVERB SLAG   	 CONTROL FURNACE REVERB  SLAG
      FIGURE B-2 Comparison of Reverberatory Slag Production- Test and Control Furnaces -
                                         August  1992


   Different figures are given for lead and slag production for each month of the  investigation.  Each figure
   contains  a statistical analysis of each month's production based on which furnace the test material was Fed.
   For example,  if the reverberatory  furnace was being fed with test material, then the analysis of variance
   was performed on the reverberatory slag and lead produced.

   3.3.2.1 August

   Figures B-2 and B-3 show  that test material processed through the reverberatory furnaces in August
   generated a significant statistically  increase in lead and slag productions. This  was an unanticipated result,
   since the test  material purportedly contained a lower concentration of lead than the regular feed. No
   adequate explanation was found, except perhaps that the test feed material could be processed faster than
   the regular feed, thereby increasing overall furnace throughput.
                                              49

-------
                           ANALYSIS OF VARIANCE (ANOVA)
VARIABLE (EXPANATION)
TEST CONTROL
FURNACE FURNACE
x1, x2 (AVERAGE DATA VALUES) 1 .09 1 .00
s1 , s2 (STANDARD DEVIATIONS) 0.15 0.10
n1,n2 (NUMBER OF DATA) 25 21
t1 , t2 (FOR 90% CONFIDENCE LIMIT) 1 .66 1 .70
s (STANDARD DEV. ACROSS ALL DATA) 0.14
z = ts ((n1+n2)/(n1 n2))A .5
D= abs(x1 -x2)
Signif. difference iff D > Z:
Conclusion:
0.07
0.09
Significant difference
x2 - xl = -0.09 ± 0.06
             AUGUST REVERBERATORY LEAD PRODUCTION
§,
s
5
                                                 •*•
ft	3*5
                                                                       22  23  24
               4   C  •   7   •   •   10  11  12  13  14

                                 DAYS PROCESSING*

             -TEST MATERIAL REVERB LEAD 	CONTROL FURNACE REVERB LEAD
     FIGURE B-3 Comparison of Reverberatory Lead Production- Test and Control Furnaces -
                                    August 1992


   3.3.2.2  September

   The statistical analyses for the reverberatory lead and slag production in September (figures B-4 and B-5)
    ielded the same quantitative results as in Agiust, with statistically significant increases in the reverberatory
                                  rn
   throughput rates.
                                        50

-------
                             ANALYSIS OF VARIANCE (ANOVA)
VARIABLE (EXPANATION)
xl, x2 (AVERAGE DATA VALUES)
s1, s2 (STANDARD DEVIATIONS)
n1, n2 (NUMBER OF DATA)
t1,t2 (FOR 90% CONFIDENCE LIMIT)
s (STANDARD DEV. ACROSS ALL DATA)
Z = ts ((nl + n2)/(n1 n2)) A .5
D = abs(x1 - x2)
Signif. difference iff D > Z:
Conclusion:
TEST CONTROL
FURNACE FURNACE
1.24
0.34
32
1.64
0.31
0.14
0.24
Significant difference
x2 - xl = -0.24 ± 0.12
1 .00
0.23
26
1.65


            SEPTEMBER  REVERBERATORY  SLAG  PRODUCTION
  a
Q
o
                      *  1
                                   DAYS PROCESSING*
               -TEST MATERIAL REVERB SLAG     	 CONTROL FURNACE REVERB SLAG
      FIGURE B-4 Comparison of Reverberatory Slag Procfuctton- Test and Control Furnaces -
                                     September 1992


  3.3.2.3 October

  Figures B-6 and B-7, which show October blast furnace lead and slag production, indicate that the average
  amount of lead produced in the furnace fed test feed was statistically higher than that produced than that
  in the control. This difference was most probably due to a higher throughput caused by the use of the test
  material.  There was no significant difference  demonstrated in the amount of slag generated in October
  between the furnace fed test materials and the control furnace.
                                           51

-------
                             ANALYSIS OF VARIANCE (ANOVA)
1 VARIABLE (EXPANATION)
xl, x2 (AVERAGE DATA VALUES)
31, s2 (STANDARD DEVIATIONS)
n1 , n2 (NUMBER OF DATA)
t1,t2 (FOR 90% CONFIDENCE LIMIT)
TEST
FURNACE
1.14
0.16
29
1.64
CONTROL
FURNACE
1.001
0.11
25
1 .66 !
           s (STANDARD DEV. ACROSS ALL DATA)      0.15	
           Z= ts  ((nl + n2)/(n1 n2)) ~.5                0.07
                     -jc2)  _         _   		i	JL14  _  _____
                       Sign¥ differehcelff D"> Z:  Significant  difference
                                    Conclusion:   x2  - xl = -0.14 ± 0.06
            SEPTEMBER  REVERBERATORY  LEAD  PRODUCTION
ra

I
Q
EL

9"
                                    DAYS PROCESSING*
           -TEST MATERIAL REVERB LEAD     	CONTROL FURNACE REVERB LEAD
     FIGURE B-5 Comparison of Reverberatory Lead Production- Test and Control Furnaces -
                                     September 1992


  3.3.3 Overall Blast Slag Production

  Since blast slag is costly to dispose of, an increase in blast slag production would cause a commensurate
  increase in costs. The amount of blast slag produced during each shift was determined based on Exide's
  daily production reports and compared for the furnace systems fed test and regular feed. Table B-7
  presents an ANOVA analysis for the  blast slag production during the three month  investigation. The
  analysis showed that there was  no significant difference  demonstrated between the  average test furnace
  slag production and the average control furnace slag production. Therefore, it was concluded that the use
  of the test feed would  not cause a significant increase in disposal costs.


                                            52

-------
                             ANALYSIS OF VARIANCE (ANOVA)
TEST
VARIABLE (EXPANATION) FURNACE
x1,x2 (AVERAGE DATA VALUES)
s1 , s2 (STANDARD DEVIATIONS)
n1, n2 (NUMBER OF DATA)
t1,t2 (FOR 90% CONFIDENCE LIMIT)
s (STANDARD DEV. ACROSS ALL DATA)
Z = ts ((n1 +n2)/(n1 n2)) A .5
D = abs(x1 - x2)
Signif. difference iff D > Z: No
Conclusion: x =
0.95
0.15
16
1.75
0.13
0.08
0.05
difference
0.97 ± 0.04
CONTROL
FURNACE
1.001
0.10
16
1.75

demonstrated
               OCTOBER  BLAST  FURNACE SLAG PRODUCTION
m
jj)
                           -*-
-4-
                                   DAYS PROCESSING'
                TEST MATERIAL BLAST SLAG      	  CONTROL FURNACE  BLAST SLAG
     FIGURE B-6 Comparison of Reverberatory Slag Production- Test and Control Furnaces -
                                     October 1992


  3.3.4 Sulfur Dioxide Emissions

  CHMR did not study the sulfur dioxide emissions during the large-scale investigation because the
  preliminary investigation revealed that the emissions did not change  significantly when test material was
  processed through the furnaces and the emissions are well controlled by Exide's  scrubber system
  Therefore, CHMR assumed that the sulfur emissions would remain relatively constant, and did not obtain
  or analyze data on them. Plant  personnel indicated that no extraordinary exceedances of permit conditions
  occurred during the three months that the tests were performed.
                                          53

-------
                            ANALYSIS OF VARIANCE (ANOVA)
VARIABLE (EXPANATION)
x1,x2 (AVERAGE DATA VALUES)
s1, s2 (STANDARD DEVIATIONS)
n1, n2 (NUMBER OF DATA)
t1, t2 (FOR 90% CONFIDENCE LIMIT)
s (STANDARD DEV. ACROSS ALL DATA)
Z= ts ((n1 + n2)/(n1n2))A.5
D = abs(x1 - x2)
Signif. difference iff D > Z:
Conclusion:
TEST CONTROL
FURNACE FURNACE
1.25
0.22
20
1.71
0.23
0.11
0.25
Significant difference
x2 - x1 = -0.25± 0.10
1.00
0.16
23
1.66
i
I

              OCTOBER BLAST FURNACE LEAD  PRODUCTION
I
o.


3"
i — i — t
                               t — 4-
                                  DAYS PROCESSING*

               TEST MATERIAL BLAST LEAD     	  CONTROL FURNACE BLAST LEAD
     FIGURE B-7 Comparison of Reverberatory Lead Production- Test and Control Furnaces-
                                     October 1992


  3.3.5  Calcium

  Several loads of material at the site contained up to 50 percent calcium. Small quantities of such materials
  could be blended with Exide's regular feedstock material. However,  it is not possible for Exide to process
  large quantities of such material through its blast or reverberatory furnaces, as such materials tend to
  impair furnace production.
                                         54

-------
                                 TABLE  B-7
           ANOVA Analysis of Blast Slag Production - August -October 1992
VARIABLE (EXPANATION)
x1,x2 (AVERAGE DATA VALUES)
s1 , s2 (STANDARD DEVIATIONS)
n1, n2 (NUMBER OF DATA)
t1,t2 (FOR 90% CONFIDENCE LIMIT)
s (STANDARD DEV. ACROSS ALL DATA)
Z = ts ((n1 +n2)/(n1 n2))°-5
D = abs(x1 - x2)
Signif. difference iff D > Z:
Conclusion:
TEST CONTROL
FURNACE FURNACE
0.87
0.44
60
1.64
0.44
0.129
0.128
1.00
0.43
65
1.64

No difference demonstrated
x = 0.94 ± 0.06
ALL PRODUCTION VALUES HAVE BEEN NORMALIZED TO 1 BY DIVIDING THEM BY THE "NORMAL FEED"
                    TO PROTECT EXIDE CONFIDENTIAL INFORMATION
                                    55

-------
                  APPENDIX C
       THE USE OF SECONDARY SMELTING
TECHNOLOGY TO RECLAIM  LEAD FROM IRON-SHOT
          BRIDGE BLASTING MATERIAL
    Description of Evaluation and Results and Discussion
                  November, 1993
                       56

-------
                                      1.0 INTRODUCTION


The  Pennsylvania Department  of  Transportation (PennDOT) uses iron shot abrasive material to blast old
paint from some state bridges.  PennDOT collects the spent material and stores it in 55 gallon drums for
disposal. CHMR obtained 16 drums (approximately 6.5 tons) of the blasting material from PennDOT  to
perform a qualitative  evaluation to determine if the  material could be processed through  a secondary lead
smelter for lead recovery. The main goal of the investigation was to determine if the  material could be
processed without causing any mechanical or production problems in the furnaces at  Exide's secondary
lead  smelter in Reading, PA.  The material used was from a bridge in Belle Vernon, PA.  CHMR observed
the modifications, if any, that were necessary to process the material in the most efficient manner.

This  appendix  details the evaluation conducted  on  iron  shot abrasive  material  used  by the Pennsylvania
Department of Transportation (PennDOT) to blast the paint from a bridge in Belle Vernon, PA.
                                               57

-------
                                      2.0 METHODOLOGY

The material arrived at the smelter in sixteen 55 gallon drums. The material was  inspected by Exide
personnel upon its arrival at the site, and they determined that the material contained too  much moisture,
which was anticipated to cause problems in the reverberatory furnaces. Plant personnel advised that  the
material, including the barrel, be placed directly into Blast Furnace #2. The other blast furnace (#1) was
processing regular feed, and this was  to be used  as  a control furnace.

Approximately 4 hours into the experiment, CHMR personnel at the site were informed  that the control
furnace had been fed with  a different  type of "typical" feed material than the test furnace. This precluded
CHMR from making any direct comparisons between the two blast furnaces. This was later verified upon
analysis pf the lead produced by each blast furnace prior to processing any test material.  Even before
the experiment, blast furnace #2 was producing lead that was significantly higher in antimony, arsenic, and
tin. CHMR decided to compare the production during  the experiment with the production in the same
furnace before  processing the  test material.

A front-end loader was used to feed the barrels into the  blast furnace at the rate of one barrel per charge,
with the furnaces being charged approximately twice every hour. All  16 of the barrels were fed into the
test furnace approximately 7 hours after the start of the experiment.   Residence time  in the furnaces
ranges up to 3 hours. Therefore,  all test material  was processed roughly 10 hours  after  feeding the  first
barrel. Furnace operating parameters, such as back pressure and air and oxygen rates, were recorded
and blast furnace slag samples were  collected by CHMR personnel approximately every  hour.

The material obtained from PennDOT  varied  in size and overall  composition. A composite sample of  the
blasting material was obtained by removing some of the material from each  barrel  prior to processing
through the blast  furnace. The material was dirty  brown in color with  visible blue-green specks in it. The
specks were most likely paint from the bridge. The sample also seemed to contain some dirt and small
wood pieces. Table C-1  provides the  analysis for the composite sample of the material  as received.
                                           TABLE C-1
                                PennDOT  BLASTING  MATERIAL
Parameter
Iron
Calcium
Lead
TCLP Lead
Total Sulfides
Other
Composition
39.7 to 63.4%
1.8%
3.2%
2.5 mg/L
7.0 mg/kg
31.6 to 55.3%
These results show that the main constituent of the blasting material is iron. The lead concentration is
relatively low compared with reverberatory slag, which is typical blast furnace feed and which contains
between 60 and 70 percent lead. The blasting material is not TCLP hazardous for  lead,  as the test yielded
a value less than 5 mg/L.
                                               58

-------
                                3.0 RESULTS AND DISCUSSION
CHMR obtained daily production sheets,  sample results, and  other general information  about furnace
performance from Exide  personnel and through direct observation in order to evaluate the processing of
the bridge blasting material through the blast furnaces at the smelter.
3.1
TEST MATERIAL
A composite sample of the 16 drums  of the abrasive blasting material was collected prior to testing.
test material was low in lead (3 to 4 percent) compared to typical blast feed, which averages 65 to 70
percent lead. The main component in the material is iron, since it is an iron shpt abrasive blasting
material. The  iron  is assumed to  be beneficial to the blast furnace performance since iron is usually added
to the furnace as  a fluxing agent. The 55 gallon barrels that contained the blasting  material also  provided
iron in the furnace.
3.2
FURNACE  PERFORMANCE
Discussions with plant management and furnace operators indicated that the test  material did not  cause
any back-ups or other mechanical problems in the blast furnace.  The observed results  were expected
since the amount of material  being fed into the furnace was very small compared to the amount of typical
feed. Plant personnel also mentioned that the smelter should  be able to accept  other iron-shot based
abrasive material. However,  they can not accept other types of  blasting material that are silica based
(such as "Black Beauty")  because a high silica content has the potential to cause  problems in the furnaces.
3.3
LEAD AND SLAG QUALITY AND PRODUCTION
The amount and nature of the slag and lead produced by the furnace are critical experimental parameters.
The quality of the lead is important since the  lead is the marketable product from the smelter. The blast
furnace slag is one of the waste streams from the smelter, and disposal is costly.

3.3.1  Lead  Quality

The results of the lead analyses are presented in Table C-2. The analyses were  performed on-site by
Exide personnel  using  Spectrometer Lab Test 201 equipment. This equipment determines the amounts
of trace metals  in the lead sample. The "Lead Before Experiment" are samples taken from  each blast
furnace prior to  processing the test material. These initial samples show that the  lead  produced in blast
furnace #1 contains significantly different amounts of antimony, tin, arsenic, copper, and cadmium than
the lead produced in  blast furnace #2. This was due to the different feed piles that were being used for
each furnace, according to Exide personnel. The  difference in the feeds is what led CHMR to abandon
furnace #1 as a valid control  furnace.
                                           TABLE C-2
                           TEST  MATERIAL BLAST LEAD ANALYSIS

LEAD BEFORE EXPERIMENT:
BLAST # 1 03:05 PM
BLAST #2, 03:05 PM
TEST MATERIAL BLAST LEAD:
BUST #2,04:00 PM
BLAST #2,05:35 PM
BLAST X2. 07:00 PM
MEAN TEST BLAST LEAD:
Pb^
9.636
8,568
8,566
10.236
11.243
... — i
1.5001
Sb Sn
1.95 0.43
5.08 1.14
5.08 1.17
5.15 1.08
4.62 1.00
4.95 1.08
± ±
0.32 1 0.09 1
L A»
0.08
0.47
0.44
0.42
0.25
0.37
07121
Cu
0.45
0.33
0.31
0.28
0.28
0.29
•4-
OX)2I
Ni
0.04
0.04
0.04
0.03
0.02
0.03
o!bi
Cd
0.15
0.57
J.
0.53
0.46 1
0.35
0.44 i
0~10I
Ca
0.11
0.11
0.01
0.10
0.10
0.07
•4-
OX«I
So
001
0.00'
0.01
0.01
0.01
0.01
oJbo
s
0.03
0.05
0.04
0.03
0.03
0.03
4-
OXM
Al
o.or
0.01
0.00
0.02
0.02
OA A
.01
± '
0.01>
                                              59

-------
 The section in Table C-2 labeled "Test Material Blast Lead" refers to the samples taken from the test
 furnace during the processing of the abrasive blasting material. The "Lead Before Experiment"  are.initial
 samples taken prior to testing.   The table shows no significant difference, based on a 90 percent
 confidence limit,  between the metals concentrations taken  before and during  the  experiment.

 3.3.2  Slag  Quality

 Table C-3 provides the analyses of the slag from the test blast furnaces. The results from blast furnace
 #1 were not used for the  evaluation. CHMR decided to concentrate on the slag taken from blast #2 the
 test furnace, to see how the  composition of the slag changed over the course of the evaluation.  An  initial
 slag sample was taken from  the test furnace prior to testing, followed by five additional samples at various
 times during the  processing of the test material.  These samples were composites of two to three furnace
 taps.

                                           TABLE C-3
                                 ANALYSIS OF  SLAG SAMPLES
Sample
Initial
1
2
3
4
5
% Pb
3.75
5.10
3.90
2.45
3.55
6.25
%Fe
38.7
44.7
40.8
42.5
46.9
47.4
Reactive Sulfides !
1.12 ppm i
ND* '
ND* i
0.23 ppm ,
0.24 ppm !
0.25 ppm
 The data indicate that the test material  had some small effects on  the composition of the slag. The
 percent iron in the slag showed a slight increase, which may be due to the high iron content of the test
 material. The reactive sulfides present in the slag  were slightly lower during the processing of the test
 material.

 3.3.3  Slag and Lead  Production

 It is difficult to make a determination about the production of lead and slag since the material was only
 being fed for a 7 hour period.  CHMR obtained Exide's daily production sheets from 9 days before the
 evaluation  through the day after. The production sheets indicated that there was basically no affect on
 the amount of lead and slag produced during the test when compared  to production  data from before the
 test. CHMR concludes this is because of the relatively low feed ratio  (10 percent by weight) of the test
 material to the furnace.
3.4
SULFUR DIOXIDE EMISSIONS
CHMR did not obtain sulfur dioxide emissions data for this evaluation.   The  iron-shot abrasive  blasting
 material was initially  low in sulfides (7 ppm) and was not expected to  raise the sulfur dioxide emissions.
 Previpus  evaluations conducted with materials containing 2 to 3 percent sulfur showed  no effect on
 emissions, which are well controlled.

3.5    FURNACE  PARAMETERS

Certain furnace parameters, such as  oxygen  and air usage, and furnace  back  pressure, were monitored
during the evaluation, and the results are given in Table C-4. The amount of oxygen needed in the test
blast  furnace was increased  slightly (approximately 100 ft3 per hour) after  roughly  3 hours because of the
                                               60

-------
test material. Air usage did not fluctuate at all, and back pressure seemed to behave normally.  There
were no reports  of any build-ups or other complications in the furnace that could be attributed to the test
material.
                                        TABLE C-4
                     TEST BLAST  FURNACE  OPERATING PARAMETERS

TIME
BLAST AIR BLAST O2
(ft3/min)
12:30PM 1000
01:00 PM 1000
01:45 PM, 1000
02:40 PM 1000
03:00 PM
03:40 PM
04:30 PM
05:00 PM
06:00 PM
07:00 PM
1000
1000
1000
1000
1000
1000
BACK
(fP/hr) . PRESS (psi).
4500
4500
4500
4500
4600
4600
4700
4700
4600
4600
1.88
1.88

COMMENTS
START FEEDING AT 12:45 PM
FEEDING 1 BARREL PER CHARGE
1 .88 ONE CHARGE PER HALF HOUR
1.75
1.81
1.94
1.63
1.81
1.69
2.06





LAST BARREL AT 07:00 PM
                                             61

-------
                                      4.0 CONCLUSIONS

Based  on the study, CHMR concluded the  following:

        The test material was fed to the furnace at  a feed ratio of approximately 10 percent of the typical
        feed that is processed through the  smelter.  No  effect was found on lead and slag production and
        quality,  production  costs, sulfur dioxide emissions,  and furnace  performance.

        The material can be easily fed into the blast furnace. The blasting material arrived in 55 gallon
        drums,  and were charged directly into the furnace when  processing this material.

        Exide plant management believe that they  can accept iron shot abrasive  blasting material.  They
        cannot  accept silica-based  blasting material.

        Costs of processing the material in  a  secondary lead smelter are estimated to be below $150 per
        drum.

These  conclusions were based on one relatively short term test, with a relatively small amount of material
processed. CHMR recommends additional testing and further monitoring of daily production data to
determine  if the blasting material has adverse effects on the slag and lead  production and to  better
determine the  process economics.
                                               62

-------
                               APPENDIX D
RECLAMATION OF LEAD FROM BATTERY CASE MATERIALS FROM THE HEBELKA SITE





              Description of Evaluation and Results and Discussion







                              February 5, 1992
                                   63

-------
                                      1.0 INTRODUCTION


The Center for Hazardous Materials Research (CHMR) and Exide/General Battery Corporation (Exide)
engaged in  a joint research study to determine the feasibility and  economics of using  Exide's
secondary lead smelters for the recovery of lead  from lead-containing materials from Super-fund sites
and other facilities. As  part of that project, CHMR/Exide  processed approximately 8 tons of battery
case  materials from  the Hebelka Corporation  (Hebelka) site in  Upper Macungie Township,
Pennsylvania.

The primary  purpose of the evaluation  was a  qualitative  determination of whether  or not battery case
materials have negative affects on the  reverberatory furnaces when the size  is reduced significantly.  A
previous investigation showed  that large  pieces of battery cases slow the  reverberatory furnace
production. The Hebelka Superfund site was originally an auto salvage yard containing approximately
1,000 cubic yards of rubber battery case  material from an unknown battery breaker source.  The
materials consisted of large broken pieces of  rubber and  polypropylene battery cases.

CHMR/Exide  received permission in January  1992 from Patrick Augustin, the EPA Project Officer for
the research, and Fred  McMillan, the Hebelka Remedial Project Manager from EPA Region III, to
proceed with the evaluation. The material was processed on February 5, 1992.

The main conclusion from  the evaluation was  that the battery case materials, after being  milled to less
than 1/4 inch,  could be successfully fed  to the  reverberatory furnaces at a weight ratio of at least 17%.
                                                64

-------
                              2.0 DESCRIPTION  OF  EVALUATION


The purpose of the evaluation was to determine if reducing the size of battery case  materials affects
reverberatory furnace  performance.  The Hebelka Super-fund site in Upper  Macungie Township,
Pennsylvania, was used  as the source of these materials. The materials  were processed over a five
hour period  at Exide's Reading,  Pennsylvania,  secondary lead smelting facility.

2.1       RECLAMATION PROCESS

The reclamation of lead from Superfund and  other lead-containing  materials is based on existing lead
smelting procedures.  The material are first collected or excavated. Next, they may be preprocessed
to reduce particle size, and to remove rocks, soil,  and other  debris.  The  materials are then  transported
to the smelter. An overview of the reclamation  and smelting process can be found  in the main report.

2.2     EXPERIMENTAL  DESIGN

The main objective of the evaluation was to feed Hebelka material  to the  furnaces at a known feed
ratio and  determine if the material  significantly  changed furnace  operation or  parameters. This was  a
short term test lasting only five hours, but the intention  was to see  if reducing the size of the battery
case material would allow it to  be  processed in the  reverberatory  furnaces. During the Tonolli
experiment,  one of the conclusions  was that large battery case pieces (up to  14") cause build-ups in
the reverberatory furnaces. This is  because the larger  pieces burn more  slpwly.  Smelter management
determined that a relatively short term test would be sufficient to detect buildups within the
reverberatory  furnace.

The material from the Hebelka site was reduced in size in a hammermill  until it passed through a V*
inch screen. After size reduction, the material was fed to one reverberatory furnace. No test material
was fed to the blast furnaces, as  the ability of blast furnaces to reclaim lead from battery case material
was evaluated  in a previous study  (Tonolli). The second reverberatory furnace was fed typical
material.   Conducting the test in this manner allows  for comparison of the  operation of the "test"
furnace with the "control" furnace.

During the evaluation, the operating parameters (fuel usage,  oxygen usage, slag production, lead
production, etc.) for each set of furnaces were  obtained,  m addition, samples 9? slag  and  lead were
obtained  from each furnace to be used to determine  effects on production quality.

2.3     EXPERIMENTAL MATERIAL

The Hebelka material  processed  during this evaluation  consisted primarily of chunks of rubber battery
cases, ranging in size from a fraction of an inch to full-sized (approximately  12-inch by 8-inch x 6-inch)
battery cases. The cases were black in color, and  appeared to be  a mixture of ebonite rubber with
some polypropylene cases. Much  of the material was covered with a thick reddish-purple sludge,
which contained approximately 80% of the  lead. Tests of the material showed  average concentrations
of 14.7%  lead. The composition of the material is further characterized in Table D-1.

2.4    CHRONOLOGY  OF THE  EVALUATION

The following represents  a chronology of the  activities  conducted in support of the evaluation between
January 24  and February  5, 1992.

2.4.1 Material Acquisition (1/24/92)

Eight tons of the battery case material were excavated  and  loaded  in two  trucks  by an  EPA contractor.
After the excavation and  loading of the  material, the equipment and  trucks were decontaminated under
EPA supervision. The material was transported to Exide's smelting facility weighed, and then stored
in an area isolated from other feed  material.
                                                65

-------
2.4.2 Size  Reduction (2/5/92)

The waste battery case material varied in size between a fraction of an  inch and  large pieces  up to 14
inches.  Based on  a  previous experiment with  rubber battery case  material  from the Tonolli Super-fund
site,  it was determined that rubber battery case material would need to be  reduced in size prior to
processing the material.

The  material  leaving  the hammermill ranged in size from a fine dust to  a particle size around  %  inch.
The  material  was  collected in  cubic yard boxes and mixed on-site with  regular feed  material before
processing. The material in  each  box weighed approximately  800  pounds.

2.4.3 Processing  in  the  Furnace (2/5/92)

The  regular  reverberatory furnace feed consisted  of spent battery parts, lead oxides,  sludge and  other
lead containing material, mainly from Exide's sink/float separation system. The rubber battery cases
were  mixed with regular feed material at a  17% weight ratio (e.g.,  17  pounds of material  to 83 pounds
of regular feed). The mixed material was fed into reverberatory furnace #1.  Reverberatory furnace #2
served  as the experimental control. The material was processed  between 12:20  PM and 5:20 PM on
February 5,  1992.

During the experiment, reverberatory furnace #1  was tapped twice for slag. The  slag from the furnace
flowed well and  there was no  noticeable build-up within the furnace.  CHIVTR  personnel continued to
monitor the  furnace  performance until  7:30 PM, with no problems  noted in  the furnace.
                                                66

-------
                                3.0 RESULTS  AND DISCUSSION
 In order to assess the viability of the process, CHMR/Exide  recorded the settings of various plant
 parameters, the  production figures  for both reverberatory furnaces, and stack parameters.  In addition,
 CHMR obtained  samples of the input  material, and output slag and  lead.  The sampling was  conducted
 in accordance with the EPA approved Quality Assurance Project  Plan  (QAPP). The results from the
 sampling and analysis  are  presented and  discussed below.

 3.1 TEST MATERIALS

 The test material was analyzed for lead, silica, sulfur,  carbon, and iron  concentrations, as well as bulk
 density, and heat value. Table 1 shows the results of analytical tests on the test materials. The
 results for silica  and sulfur  are below the thresholds at which the  material  would impair the furnaces.
 The carbon  and  iron percentages are  favorable for smelting.  The amount  of lead  in the material
 (14.7%) is  considerably below that  of  normal  reverberatory furnace feeds,  which average about 60%
 lead.

                       Table  D-1. Hebelka Battery  Case Material Analysis
Sample
#

2
3
Average
Pb
(%)
13.9
18.4
11.7
14.7
S
(%)
3.3
1.3

2.3
Si02 (%)
5.2
4.2

4.7
C
(%)
52
60

56
Fe
(%)
0.45
0.36

0.41
Density
(Ib/ft3)
58
51

55
Heat
(BTU/lb)
9670
7820

8750
3.2 SLAG AND LEAD  PRODUCTION AND QUALITY

The amount and  nature of slag and  lead produced by the furnaces were critical experimental
parameters. The amount and quality  of lead produced is important because  lead is the salable  product
from the smelter. The reverberatory slag characteristics also important,  because this slag  is used  as
feed material for the blast furnace.

Composite  slag samples were taken as the slag was being  tapped from  the furnaces throughout each
shift from reverberatory furnace #2. Grab samples of sjag were taken from furnace #1. The molten
slag samples were collected by  the Exide operators by inserting  a shovel into the furnaces and
extracting  the sample, in accordance  with the QAPP. The results of the  slag analysis are  presented  in
Table D-2.

The amount of lead  production  was determined by collecting Exide's  daily  production reports, which
detail the entire smelter activity for each day. The quality of the  lead was determined through analysis
with a  Spectrometer  Lab Test  100. This analyses, which  is  performed on-site by Exide personnel,
provides the amount of  several  trace metals in lead samples taken from the furnace. The results from
these tests can be seen in  Table D-3.

Performing a paired  two-sample T-test  for  means for each metal in the table revealed  that only the
antimony showed a  difference  between the two means. The test was performed with a 95%
confidence level.
                                               67

-------
            Table D-2. Composition of Slag Samples from  Reverberatory Furnaces
Sample
1
2
3
4
5
6
!f? •*• ^'v ' %
«; *• „ "•
' Sample
7
8
Furnace
Test
Test
Test
Test
Pb (%)
72.0
42.2
62.4
73.1
Test 59.1
Test
^tti&vtttti*'*
f\%*f**f!J*r
Furnace
Control
Control
'&vefag.
Pb (%)
S (%)
8.2
1.3
7.1
10.5
7.3
6.9
'', && ^
;//, >">»* JJj
S (%)
52.5 6.5
60.8
6.1
Sb (%)
3.0
5.8
2.8
1.5
2.7
3.0
*4 -
-------
                              Table D-4. Furnace Parameters During Test.

Time
13:30
14:00
14:30
15:00
15:30
16:00
16:30
17:00
17:30
Oxygen usage (cfm)
Test
1500
1500
1500
2100
2200
2200
2200
2000
2100
Control
1500
1900
1700
1800
1800
1800
1900
1800
1800
Gas usage (rel. units)
Test
6.8
6.8
6.8
6.8
6.8
6.8
6.8
6.8
6.8
Control
8.0
6.0
8.0
6.0
6.0
6.0
6.0
6.0
6.0
3.4.1 Sulfur Dioxide Emissions

In order to feasibly process the Hebelka material, it is important that the test materials do not cause an
increase in sulfur dioxide (S02) emissions above Exide's permitted emissions limits of approximately 110 parts
per million (ppm). No such increase was anticipated because the concentration of sulfur in the normal furnace
feed is about 1  to 2%, and also because Exide has a sulfur dioxide control system. However, CHMR/Exide still
monitored  sulfur dioxide  emissions to determine  if an increase occurred.

CHMR/Exide  obtained data concerning  sulfur dioxide emissions from the facility's  SO?  Continuous  Emission
Monitor (CEM).  Average and initial data values were collected by the operator and CHMR/Exide project
personnel  on duty during each shift.  Each stack system  is connected to the corresponding blast and
reverberatory furnaces. The average stack emission in system #1, to which the test material was fed, was 56
ppm,  while the  average stack  emission in system #2 was 78 ppm.  Thus, the emissions remained considerably
below the permit levels of 110 ppm.

3.4.2 Calcium  Sulfate Sludge

During each shift, specific gravity  measurements of slurry generated from the air  emission control equipment
(scrubbers) were taken by the operator on duty. The specific gravity is related to the calcium sulfate
concentration  in the slurry, and therefore gives  a measure of total sulfur uptake in the sludge.   Slurry  specific
gravity measurements for  both  stacks averaged  1.25,  which indicates  no significant difference  between the
slurry produced  in the furnace system fed the Hebelka  material and that produced in the system fed only
normal feeds.

At the end of each shift, the arrount of slurry was calculated by counting the number of truckloads transported
from the scrubbers to the on-site sludge dewatering facility. No increase was found in the number of
truckloads  produced  each shift.
                                                 69

-------
                          APPENDIX E
RECLAMATION OF LEAD  FROM DEMOLITION MATERIAL FROM A HUD
                          RENOVATION
            Description of Evaluation and Results and Discussion
                           December 1991
                               70

-------
                                      1.0 INTRODUCTION
The Center for Hazardous Materials Research (CHMR) and Exide/General  Battery Corporation (Exide)
engaged  in a joint research study to determine the  feasibility and  economics of using Exide's
secondary lead smelters for the recovery  of lead from lead-containing materials found  at Superfund
sites and other sources. As part of this study, CHMR/Exide processed demolition material (primarily
wood) from the renovation of  a  women's shelter in  Montgomery County,  PA.

One common, but often overlooked, source of lead is demolition material from residential housing
coated with lead  based  paints.  Many houses, especially  older ones,  have interior and exterior wood
which can  contain lead in excess of 1%.  The current treatment for lead-containing demolition waste is
to place it into sanitary landfills  with other municipal wastes. As an alternative to landfilling, CHMR and
Exide evaluated  the potential  for processing lead-containing demolition material in a  secondary lead
smelter.

The demolition material is from the front and back porches of the Laurel House,  a women's shelter in
Montgomery County, PA. The deteriorating porches were coated with lead based paint. The
Montgomery County Housing  and Community Development (MCHCD) Office contracted an
environmental  firm to perform the necessary abatement.  Nearly five tons of lead-containing waste was
generated.

The main goal of this short term experiment was to determine the effects that a wooden feed would
have on the reverberatory furnaces.  After  receiving  consent from the EPA,  the demolition material was
transported  to  Exide's secondary lead smelter in Reading, PA, and accumulated  until December 16,
1991, when the material was  processed through  the smelter.
                                               71

-------
                             2.0 DESCRIPTION OF EVALUATION
The  purpose  of this evaluation was to determine the affects on furnace production that  a  wood-based
feed would have. Material was acquired  from  the Laurel  House, a woman's  shelter in Montgomery
County, PA. The demolition materials were processed over a ten hour period at Exide's Reading, PA
smelter.

2.1  RECLAMATION  PROCESS

The  reclamation  of lead from  Superfund  and other lead-containing materials is  based  on existing  lead
smelting procedures. The material are first collected or excavated. Next,  they may be preprocessed
to reduce particle size, or to remove rocks, soil, and other debris, The materials are then transported
to the  smelter. An  overview of the reclamation and  smelting process  can  be found in the main report.

2.2  EXPERIMENTAL DESIGN

The  main objective of this evaluation was  to process  the  demolition  material in  the reverberatory
furnaces at a known feed  ratio and determine  if the material  significantly  changed furnace operation or
performance.  Unlike other evaluations, material was charged to both reverberatory furnaces.
Therefore, this test did not have a "test"  and "control"  furnace and so comparisons can only  be made
to determine how both  furnaces performed  with respect to each other while  processing the same feed.

The  preprocessing phase for this  evaluation involved reducing  the size of the demolition material with a
pallet shredder, and then storing  in an area separate from  other feed material at the  smelter.  During
this  evaluation, certain  operating  parameters for each  reverberatory furnace were  obtained,  including
air and  natural gas usage. Samples  of slag and lead  were obtained from the reverberatory furnaces
for analysis.

2.3  EXPERIMENTAL MATERIAL

The  demolition material consisted primarily of pieces of wood coated with lead-based paint. The
material arrived at the smelter on pallets in three to six foot lengths. The  material had an  average lead
concentration of 1.2%, and an average TCLP  lead level of 13.7 mg/l. The ash content of the material
was  determined to be  4%  by weight.

2.4 CHRONOLOGY  OF THE EVALUATION

The  following  is a chronology  of the  activities  conducted for this evaluation between November 21  and
December 16, 1991.

2.4.1 Material Acquisition

MCHCD  contacted  CHMR in early November  and expressed  interest  in working  with the lead
reclamation project. CHMR consulted with Patrick Augustin of the EPA, who agreed that the material
could be processed as part of the research project. Starting  on  November  21,  the environmental
contractor responsible  for the  lead abatement  transported  several pallets  of the demolition material to
the smelter in Reading, PA. Once at the smelter, the  material was weighed, processed through a
                                               72

-------
 pallet shredder,  and stored separate  form  other smelter feed  material.

 2.4.2 Day One (12/15/91)

 CHMR personnel arrived at the site and were introduced to smelter management and supervisors.
 CHMR personnel also  received health and  safety training regarding  the operations and equipment at
 the smelter.

The density of the demolition material was  determined by weighing a known volume of the material
 This procedure was duplicated seven times, and  the average density was found to be  15.7 Ibs/ft3.

Three composite sample of the initial  demolition  material were collected  in  accordance with section  3.6
 of the Quality Assurance Project Plan (QAPP). Grab samples of the lead and slag produced by the
 reverberatory furnaces  prior to processing any test material were  also collected.

 2.4.3  Day Two (12/16/91)

More samples of the  reverberatory lead and slag were  taken before feeding the demolition material
The test  material and  regular feed  were mixed prior to starting the experiment.

At 10:30 AM,  a mixture containing 10% by weight (50% by volume) demolition material was charged to
both furnaces. At approximately 1:30 PM, plant management noticed a buildup of material in both of
the reverberatory furnaces.  Test feed to the furnaces was suspended and  oxygen flow was increased
to try and correct this  problem.

Exide  plant management decided that the feed  ratio should be lowered to 5% by weight to  try and
 prevent any further  buildups from occurring  in the furnaces. The mixed feed was started again at 3:00
 PM and continued until 8:45 PM, with no other problems noticed in  the furnace. All slag and lead
samples taken during  the course of the  investigation were taken in accordance with the  QAPP.
                                              73

-------
                                 3.0  RESULTS AND DISCUSSION
CHMR obtained enough data to determine whether or not the material could be successfully  run at the
tested feed ratios. The test was not long enough to determine the total effects that processing the
demolition material had on  the furnaces.  The following sections give more detailed information on the
operating parameters for  the two  reverberatory  furnaces.

3.1 INPUT  PARAMETERS

CHMR personnel recorded  air flows, oxygen  volumes, natural  gas usage, and types of material
charged into the furnace. No major changes were noted in  air or  natural  gas usage throughout the
length of the experiment. The percent oxygen enrichment had to be increased for a short time to
reduce the buildups in the  reverberatory furnaces that occurred  from processing the test material at a
10% by weight mixture.  Overall the results were inconclusive:  insufficient material was processed to
adequately determine  if changes in process settings, i.e., natural gas, oxygen, were necessary to
process the demolition material.

Three samples of the test material were collected prior to the start of the evaluation, and two were
sent to separate laboratories. Table E-1 shows the composition  of the feed material.  The material has
a  lead concentration of 0.96% in  one analysis and  1.5% in  another. The average leachable  lead  is
13.7 mg/l, based on TCLP  analysis.

                            Table E-1.  Analysis of  Demolition Material
Feed
Sample
1
2
TCLP Pb
(mg/l)
11.3
16.1
Pb
(ppm)
9,594
—
Pb
(%)
0.96
1.5
Ash
(%)

4
3.2 SLAG PRODUCTION AND QUALITY

The  reverberatory slag production and quality are important concerns because the slag is used  as feed
to the  blast furnaces. CHMR acquired Exide's daily production sheets for the week of December 13
through December 18, 1991. The test appeared not to affect the slag  production  at all, however, since
the test was  short term with only 9,000  pounds processed, no conclusions can be drawn about  how
the demolition material affected the slag production.

Composite slag samples  were taken as the slag was tapped throughout each  shift. These samples
were taken by inserting a shovel into the furnace and removing the  slag, in accordance with  section
3.6 of  the QAPP. At the end of each shift, CHMR personnel collected  the samples and split them with
Exide.  The reverberatory slag samples were  analyzed for percent lead, tin, antimony,  and arsenic.
Tables E-2 and E-3 below show the analysis of the slag  samples taken before, during,  and after the
evaluation.  Although  furnace #1 showed a slight decrease in slag lead content, Exide  personnel said
that it is in the acceptable range for the reverberatory slag. Furnace #2 showed  a slight increase, but
leveled out during the evaluation.
                                                74

-------
                       Table E-2. Reverberatory Furnace #1 Slag Samples.
When
Before
During
During
After
Pb (%)
60.4
55.3
50.0
47.2
Sb (%)
3.40
5.07
1.25
6.56
Sn (%)
0.80
1.09
0.25
1.50
As (%)
0.22
0.29
4.25
0.36
                       Table E-3.  Reverberatory Furnace #2 Slag Samples.
When
Before
During
During
After
Pb (%)
51.4
66.5
69.3
66.2
Sb (%)
5.34
3.60
0.56
3.28
Sn (%)
1.52
0.66
0.06
0.62
As (%)
0.43
0.24
2.80
0.22
3.3 LEAD  PRODUCTION AND QUALITY

The production and quality of lead is an  important parameter because lead is the salable product  from
the smelting  process. CHMR anticipated  that the  demolition  material  would cause a decrease  in the
production  of lead. This would not be caused by any change in the slag, but because the demolition
material comprised much of the volume of the feed. Therefore,  any decrease would be due to the
decreased  throughput.  However, the  material was not  run  long enough to  notice any affects  on the
lead production.

Lead samples were collected throughout  the evaluation and  analyzed with  a Spectrometer Lab Test
100. This analyses, which is performed on-site  by Exide personnel, provides  the amount of  several
trace metals in lead samples taken from  the furnace. CHMR could not get this data,  however Exide
plant supervisory personnel noted  that there  was no change in  lead  quality throughout the evaluation

3.4 SULFUR

Once material is inside a  furnace, the sulfur present in the demolition material can  exit the process  by
three means:  through stack gas emissions, through the calcium  sulfate  sludge generated by the
emissions  control system,  or in the blast and reverberatory slag.

3.4.1 Sulfur Dioxide Emissions

Sulfur dioxide (S02)  emissions  cannot exceed  Exide's permitted emissions limits  of 110 ppm. S02
emissions at  Exide are constantly monitored and recorded on a  strip chart recorder. However,  at  the
time of  the evaluation, Exide was having mechanical problems with their S02 Constant  Emission
Monitor  (CEM). Plant personnel estimated that  the sulfur dioxide  levels never exceeded  100  ppm
based on the  limited data  that they could acquire.
                                                75

-------
3.4.2 Calcium  Sulfate  Sludge

Calcium  sulfate  sludge  is generated by the emissions control  equipment (scrubbers) at the smelter.
Specific gravity measurements of the slurry were taken  approximately  every  hour by Exide personnel.
The  specific gravity is related to the amount of calcium sulfate in the  slurry  and therefore allows for an
estimate  of sulfur  uptake  in the sludge. The average specific gravities  over the  course of the
experiment were 1.22 and 1.20 for furnaces 1 and 2, respectively. There was also no increase in the
daily amount of calcium sulfate sludge generated.
                                                 76

-------
                                        4.0 CONCLUSIONS
Based  on the limited  evaluation conducted, CHMR/Exide  concluded the following:

        It is technically  feasible to reclaim lead  from wood  demolition materials,  provided they are
        appropriately sized to fit in the furnaces.

        The material burns well in the furnaces, and did  not present any major difficulties based on its
        combustive properties  (i.e., did not cause  a build-up within  the  reverberatory furnaces).

        The economics  of recovering lead from such  materials are difficult to assess.  However, the
        value of the material as a feed to the smelter is minimal because it contains such a low
        concentration of lead. The use of secondary lead smelters is only likely  to be economical
        when the demolition material  is  a hazardous waste, and therefore cannot be disposed
        economically in  a municipal or demolition  landfill.
                                                77

-------