&EPA
United States
Environmental Protection
Agency
Municipal Environmental Research EPA-600/7 3-14'i
Laboratory August 1978
Cincinnati OH 45268
Research and Development
Investigation
of Advanced
Thermal - Chemical
Concepts for Obtaining
Improved MSW - Derived
Products
Interagency
Energy/Environment
R&D Program
Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1 Environmental Health Effects Research
2. Environmental Protection Technology
3 Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9 Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-143
August 1978
INVESTIGATION OF ADVANCED THERMAL-CHEMICAL
CONCEPTS FOR OBTAINING IMPROVED MSW-DERIVED PRODUCTS
by
N.L. Hecht
D.S. Duvall
B.L. Fox
University of Dayton Research Institute
Dayton, Ohio 45469
Grant No. R-804421-01
Project Officer
Albert Klee
Solid and Hazardous Waste Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Municipal Environmental
Research Laboratory, U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the U.S.
Environmental Protection Agency, nor does mention of trade
names or commercial products constitiute endorsement or
recommendation for use.
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FOREWORD
The Environmental Protection Agency was created because of
increasing public and government concern about the dangers of
pollution to the health and welfare of the American people.
Noxious air, foul water, and spoiled land are tragic testimony
to the deterioration of our natural environment. The complexity
of that environment and the interplay between its components
require a concentrated and integrated attack on the problem.
Research and development is that necessary first step in
problem solution and it involves defining the problem, measuring
its impact, and searching for solutions. The Municipal Environ-
mental Research Laboratory develops new and improved technology
and systems for the prevention, treatment, and management of
wastewater and solid and hazardous waste pollutant discharges
from municipal and community sources, for the preservation and
treatment of public drinking water supplies, and to minimize the
adverse economic, social, health, and aesthetic effects of
pollution. This publication is one of the products of that
research; a most vital communications link between the research-
er and the user community.
This report presents information resulting from a study of
chemical and thermal treatments to improve the quality of the
products derived from the organic fraction of municipal solid
waste. Processes for obtaining a carbon char and a powdered
fuel are described in depth. It is hoped that the information
provided in this report will be of assistance to researchers and
developers concerned with resource recovery endeavors.
Francis T. Mayo, Director
Municipal Environmental
Research Laboratory
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ABSTRACT
A number of resource recovery projects have been instituted
to recover fuel, energy, and mineral components from refuse.
Although a number of these programs have been effective, the
quality of the products recovered could be enhanced to improve
their marketability. The purpose of this study was to investi-
gate the potential of known processes that could improve the
quality of the fuels or other products derived from the organic
fraction in refuse.
To effectively accomplish the stated objective for this
study, a comprehensive review of processes for making refuse a
better fuel was performed. Information was obtained from the
open literature, and through personal contacts. Possible pro-
cesses for improving the quality of products from the organic
fraction derived from municipal solid waste (MSW) were deter-
mined, and descriptions were developed for each process. To
better evaluate the different processes, an analytical framework
for technical and economic assessment was developed to serve as
a guide for analysis, as well as for the information acquisition
phase of the study. The literature search identified major
thermal and chemical processes used in the pulp and paper, wood,
textile, and resource recovery industries.
This study concentrated on those processes designed to
produce a carbon char, a powdered fuel, and liquid and gaseous
fuels from the municipal solid waste. Of particular interest in
the production of carbon char were those chemical treatments
that promote char formation at lower pyrolysis temperatures.
For the production of powdered fuels, the chemical and thermal
treatments which cause cellulose embrittlement were of most
interest. For the production of gaseous and liquid fuels two
processes were evaluated: Worcester Polytechnic's hydrogena-
tion-liquefaction process and Wright-Malta's steam injection
pyrolysis process.
A major accomplishment of this project was the identifica-
tion and laboratory verification of chemical treatments for
cellulose embrittlement. As a result of preliminary laboratory
studies the basic requirements were defined for producing a fine
powdered fuel from the organic fraction of MSW. More quantita-
tive measurements of the embrittlement process parameters are
recommended. The problems which could be encountered during the
chemical treatment of shredded MSW must also be determined. The
iv
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information obtained from these studies could provide the basis
for a detailed engineering and economic analysis for a full
scale facility to produce a fine powdered fuel.
v
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CONTENTS
Foreword iii
Abstract iv-v
Figures vii
Tables viii
Acknowledgment ix
1. Introduction 1
2. Conclusions and Recommendations 3
3. Background 4
4. Literature Search 14
5. Carbon Char Production 16
6. Powdered Solid Fuel 44
7. Liquid and Gaseous Fuels From the Organic
Fraction of Municipal Solid Waste 59
References 66
Bibliography 68
VI1
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FIGURES
Number Page
1 Results of thermogravimetric analysis in a
nitrogen atmosphere 20
2 Basic flow plan for Harendza-Harinxma process. . 22
3 Modified Black-Clawson wet process 25
4 Material and energy balance based on 1 ton MSW
to the processing facility 26
5 Flow plan for a plant to convert MSW to a
carbon char 37
6 Experimental arrangement used for embrittlement
studies 46
7 Resource recovery plan to produce powdered
fuel 52
8 Cellulose hydrogenation 61
9 Flow plan for the WPI process 62
viii
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TABLES
Number Page
1 Refuse Composition 5
2 Chemical Analysis of Refuse 5
3 Paper Wastes in Municipal Refuse 6
4 Pyrolysis Reactions of Cellulose 11
5 Potential Char Promoters 18
6 Analysis of the Inert Fraction in the Carbon
Char 23
7 Material and Energy Balance Calculation for
One Ton of Municipal Solid Waste 27
8 Material Balance Calculations for a Carbon
Char Production Process 38
9 Estimated Capital Costs (1977 Dollars) 42
10 Estimated Annual Operating and Maintenance
Costs (1977 Dollars) 42
11 Potential Revenue Sources 43
12 Chemical Embrittlement of Paper Screening Study .. 47
13 Combustion Analyses of Paper Powders
(Weight Percentage) 48
14 Material Balance for a Powdered Fuel Process 53
15 Estimated Capital Costs (1977 Dollars) 57
16 Estimated Annual Operating and Maintenance
Costs (1977 Dollars) 57
17 Potential Revenue Sources 58
ix
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ACKNOWLEDGMENT
The authors wish to acknowledge the assistance of Dr. A.J.
Klee the Environmental Protection Agency project officer. Also,
they wish to express their appreciation to their colleagues at
the University for the assistance they have rendered throughout
the first year of this study: C.C. Lu, J.P. Keyes, A.A. Ghazee
and L.G. Wallick. In addition, the authors wish to acknowledge
the assistance provided by Dr. J. Harendza-Harinxma of
Lawrenceville, N.J. and Dr. H.G. Rigo of Systems Technology
Corporation, Xenia, Ohio.
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SECTION 1
INTRODUCTION
Effective refuse disposal is a problem that has perpet-
ually plagued mankind. Historically our solid waste has either
been buried or burned with little regard for the environmental
consequences. In recent years, greater emphasis has been
directed toward recovering the valuable mineral components and
energy contained in the waste. Utilization of the waste
components can reduce the environmental impact of waste dis-
posal and conserve natural resources. A number of resource
recovery projects have been instituted to recover fuel, energy,
and mineral components from refuse. Although a number of these
programs have been effective, the quality of the products
recovered could be enhanced .to improve their marketability.
The purpose of this study was to investigate the poten-
tial of known processes that could improve the quality of the
fuels or other products derived from the organic fraction in
refuse. Since cellulose products are the major constituents
of the organic fraction in refuse, it seemed likely that a
number of the processes employed in the pulp, paper, and textile
industries would have considerable potential for refuse pro-
cessing.
To effectively accomplish the stated objective for this
study, a comprehensive review of processes for making refuse a
better fuel was performed. Information was obtained from the
open literature, and through personal contacts. Possible pro-
cesses for improving the quality of products from the organic
fraction derived from municipal solid waste (MSW) were deter-
mined, and descriptions were developed for each process. These
descriptions included: (a) the techniques and procedures
required; (b) the type of industry or application in which the
process is employed; (c) the current status of this technique
(such as laboratory, pilot, or full-scale plant operation); and
(d) economic information about the process. To better evaluate
the different processes, an analytical framework for technical
and economic assessment was developed to serve as a guide for
analysis, as well as - for the information acquisition phase of
the study.
The literature search identified major thermal and
chemical processes used in the pulp and paper, wood, textile,
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and resource recovery industries. A brief summary of the
information obtained from the literature search is presented in
the background section of this report. This study concentrated
on those processes designed to produce a carbon char, a
powdered fuel, and liquid and gaseous fuels from the municipal
solid waste. Of particular interest in the production of carbon
char were those chemical treatments that promote char formation
at lower pyrolysis temperatures. For the production of
powdered fuels, the chemical and thermal treatments which cause
cellulose embrittlement were of most interest. For the
production of gaseous and liquid fuels two processes were
evaluated: Worcester Polytechnic's hydrogenation-liquefaction
process and Wright-Malta's steam injection pyrolysis process.
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SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
The technology of cellulose chemistry does provide
opportunities for processing the organic fraction of Municipal
Solid Waste (MSW) to obtain improved products. In this study
laboratory processes for obtaining a carbon char and a fine
powdered fuel have been identified. In addition laboratory
processes for liquid and gaseous fuels described in the litera-
ture have been reviewed.
Several chemical treatments for promoting char forma-
tion at lower temperatures have been determined. The patented
process developed by Dr. Harendza-Harinxma was assessed to
be impractical as a means of char production on a large scale.
A more feasible means to produce char might be by incorpora-
tion of a char promoter in the Black Clawson wet process. A
market for the char has not been firmly established. Any
market requiring rigid specifications for the carbon char
would not be satisfied due to the fluctuations in the content
of raw solid waste.
During the course of this project two processes for the
production of liquid and gaseous fuels were reviewed. Both
the Worcester Polytechnic Institute process and the Wright-
Malta Corporation process were selected because of this unique
potential. However, after review it was concluded that both
processes were not practical for implementation on large scale
at the present time.
A major accomplishment of this project was the identi-
fication and laboratory verification of chemical treatments
for cellulose embrittlement. As a result of preliminary
laboratory studies the basic requirements were defined for
producing a fine powdered fuel from the organic fraction of
MSW. More quantitative measurements of the embrittlement
process parameters are recommended. The problems which could
be encountered during the chemical treatment of shredded MSW
must also be determined. The information obtained from these
studies would provide the basis for a detailed engineering
and economic analysis for a full scale facility to produce a
fine powdered fuel.
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SECTION 3
BACKGROUND
Due to the many problems associated with the convention-
al practices of landfilling and incineration, a number of new
techniques are being developed to improve the management of
municipal refuse. The majority of these new techniques are
concerned with recovering and utilizing the valuable materials
in solid waste. Resource recovery is the term applied to the
numerous processes and systems being designed to recover compo-
nents of waste and convert them to useful products. Systems
have been developed for energy recovery; compost production;
fiber, glass and metal recovery; and alcohol and protein produc-
tion. The major emphasis has been on those processes designed
to recover the thermal energy in waste. Although many of the
systems developed have been relatively successful, the quality
and consistency of the fuel produced or the energy generated has
not been completely satisfactory. Higher quality and greater
consistency in the waste-derived fuel or energy is necessary if
it is to be marketable for large-scale usage.
The most commonly used process for recovering the ther-
mal energy in municipal waste incinerates the raw refuse
directly and uses the heat to generate steam. Steam-raising
municipal incinerators are common in Europe and Asia, and
during the past several years a number of units have been built
in the United States. In addition to direct combustion of raw
refuse, a number of processes have been developed for recovering
fuel products from the refuse. Fuel recovery is based largely
on the use of shredding, magnetic separation, and air classifi-
cation to obtain the light weight or predominately organic
solid fraction from the refuse. A few pilot and demonstration
processes have also been developed which convert the organic
fraction to a liquid or a gaseous fuel.
3.1 Municipal Refuse
Municipal refuse is a heterogeneous mixture of organic
and inorganic wastes discarded from the residential and
commercial sectors of the community. The composition of the
refuse fluctuates from day to day and season to season. An
average distribution of the components in refuse is shown in
Table 1. The moisture content of the refuse can vary from 15
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TABLE
REFUSE COMPOSITION
Components
Paper
Plastics
Rubber and Leather
Textiles
Wood
Food Wastes
Yard Wastes
Glass and Ceramics
Metal
Ferrous - 8.7
Aluminum - 0.7
Other - 0.3
Miscellaneous
Weight (%)
28.9
3.4
2.5
1.6
3.7
17.8
20.3
10.4
9.7
1.7
100.0
Organic
Fraction
to 50% but averages about 27%. A typical chemical analysis for
refuse is presented in Table 2. From 70 to 80% of the dry
weight of refuse will be organic materials, and about 75% of
this organic fraction is cellulose.
TABLE 2'
CHEMICAL ANALYSIS OF REFUSE
Components
Carbon
Hydrogen
Oxygen
Nitrogen
Sulfur
Moisture
Inert
Weight (%)
28.00
3.50
22.35
0.33
0.16
20.73
24.93
As shown in Table 1, paper is the single largest compo-
nent of municipal refuse. Food and yard wastes are the next
largest components. These wastes plus the wood and textile
wastes contribute significant quantities of cellulose to the
waste stream. A breakdown of the paper wastes found in refuse
is compiled in Table 3. The cellulose content of these products
varies from 50 to 90%.
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TABLE 3'
PAPER WASTES IN MUNICIPAL REFUSE
Type Weight %
Newsprint 40
Container and Packaging Board 22
Coarse Paper 13
Book Paper 12
Sanitary and Tissue 8
Fine Paper 4
Ground Wood Paper 1
100
3.2
Cellulose
Cellulose is a carbohydrate polymer composed of anhydro-
glucose units with the empirical formula CgHi00_. It is the
chief structural element and major constituent 3f the cell walls
of trees and of other higher plants. Cellulose is the most
abundant and versatile of all naturally occurring organic com-
pounds and plays an increasingly important part in the life of
civilized man as a component in many products that he requires
daily. It is relatively inexpensive and, unlike some other
basic raw materials, it is replenishable.
Cellulose is a linear polymer of glucose containing up
to 10,000 monomer units (molecular weight 1,500,000) linked
together by 3-l,4,D-glucosidic links. Cellulose has the same
chemical structure, regardless of whether it occurs in soft-
woods, hardwoods, flax, cotton, etc. As a result of chemical
action such as pulping or bleaching, the native cellulose may
be somewhat modified, i.e., 'the polymer chain is shortened and
the terminal group may be converted to a carboxyl group.
Certain groupings, such as carbonyl groups which may be formed
under certain conditions of bleaching (hypochlorite at pH of
about 8.0), result in an instability in the polymer which can
result in subsequent yellowing and degradation on aging.
H OH
CH2OH
H OH CH2OH
cellulose
H OH
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Cellulose is used in its natural fibrous form in paper
products and as chemical raw material for the manufacture of
cellulose derivatives (cellulose nitrate, ethylcellulose,
cellulose acetate, etc.) and regenerated cellulose products
(tire cord, viscose rayon, cellophane, etc.).
Cellulose undergoes such reactions as: (1) oxidation;
(2) depolymerization; (3) hydrolysis; (4) substitution of
hydroxyl groups; (5) reduction of end groups, etc. This range
of reactions suggests the possibility that a variety of chemical
treatments could attack cellulose and break it down in such a
manner that its value as a fuel could be enhanced.
3. 3 Fuel Recovery
3.3.1 Dry Processing
The most common method for fuel recovery is the
one which was developed in an EPA demonstration program with the
City of St. Louis and the Union Electric Company. In this pro-
cess the refuse is shredded and air-classified to separate the
light-weight materials (predominantly organic substances) from
the heavier materials (glass, metal, and other noncombustibles).
This shredded light fraction, termed RDF (refuse-derived fuel)
fluff, has been successfully co-fired with coal in a Union
Electric boiler. Several plants have been built and a number of
others are planned to produce an RDF fluff. Although each plant
may have a somewhat different processing procedure, the fuel
fraction is primarily the shredded organic materials with a
small percentage of noncombustible fines (glass, stone, metal,
dirt, etc.). The quantity of noncombustible material in the
refuse-derived fuel, as well as its moisture content and parti-
cle size will depend on the specifics of the particular process.
Also, for some of the advanced systems the concept of pelleti-
zing the RDF fluff is being studied. Fuel pellets are easier to
handle and are more compatible with many boiler designs for fuel
injection.
)
3.3.2 Wet Processing
In addition to the dry processes for recovering
the fuel fraction, Black Clawson has developed a wet process
based on papermaking technology. This hydrapulping process was
primarily designed for recovery of paper fibers but can recover
over 90% of the organic fraction. The waste is suspended in
water and mechanically broken down in size. The slurry from the
hydrapulper is mechanically dewatered to about 50% solid content.
This product has been fired in bark and bagasse-type boilers and
in a pilot study was palletized and fired in a spreader-stoker
type boiler.
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3.3.3 Powder
A proprietary process for recovering a powdered
fuel has been developed by Combustion Equipment Associates
(CEA). The air classified, shredded light fraction is chemical-
ly treated during a hot ball milling process. It is believed
that the chemical and heat treatment cause embrittlement of the
cellulose. The ball mill material is screened to 20 mesh frac-
tion. This fine powder contains about 15% inert material which
can be reduced by a second air classification. The powdered
fuel produced by CEA is marketed under the trade name Eco-Fuel
II. This material has a heating value of 7500-8000 Btu/lb, and
density of 30 lbs/ft3, a moisture content of approximately 2%
and an ash content of approximately 10%.
3.4 Fuel Enhancement Processes
3.4.1 Physical and Chemical Processes
Converting the organic fraction of refuse into a
finely powdered fuel offers a number of advantages. In powdered
form the refuse is more compatible with the fuel used in suspen-
sion fired boilers; it is more easily slurried with oil for
firing in liquid fuel units; and it is more easily pelletized
for use in moving-grate units.
A number of thermal and chemical treatments have
been identified that promote the conversion of the organic frac-
tion in refuse to a fine powder. Since the major constituent of
the organic fraction is cellulose (75%), the treatments are
based primarily on the technology of cellulose processing. Most
of these processes are chosen to embrittle or degrade the cellu-
lose by reducing the degree of polymerization. If the acid or
oxidizing treatment uses very strong chemical agents over a pro-
longed period of time, the cellulose can be transformed into a
fine powder. In addition to degradation, certain acid treat-
ments can also promote crosslinking of adjacent molecules,
which makes the cellulose rigid and brittle. Heating cellulose
in air up to temperatures of 400°F will also result in embrit-
tlement. This is achieved by crosslinking reactions between
adjacent molecules, which occur as part of the dehydration
process during extended heating. Cellulose treated with formal-
dehyde also undergoes embrittlement as a result of the formation
of oxygen bridges. The formation of ethers and esters of cellu-
lose can also be used as a means for forming powdered fuels.
Solidified cellulose ether and ester derivatives are easily
ground into fine powders.
Another means for cellulose decomposition is
acid hydrolysis. Cellulose is soluble in concentrated solutions
of sulfuric, phosphoric, and hydrochloric acids. The end
8
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product of cellulose hydrolysis is glucose. However, continued
chemical action on the glucose results in the formation of
hydroxymethylfurfural, which produces levulenic acid and formic
acid. The glucose recovered from hydrolysis can also be fermen-
ted to ethyl alcohol. The feasibility of employing this process
for large scale treatment of MSW is questionable.
Combinations of chemical and thermal treatments
can also be employed for cellulose decomposition and conversion
to liquid fuels. A number of these liquefaction processes have
been developed. The conversion of wood products to liquid and
gaseous products dates back to the early 1900's. Most commonly,
cellulose products were hydrogenated at temperatures from 300-
930°F at elevated pressures and in the presence of a catalyst.
Two recently reported processes for the lique-
faction of municipal waste were developed by the Bureau of
Mines and Worcester Polytechnic Institute. In the Bureau of
Mines process, cellulose waste is treated with carbon monoxide
and water to obtain a liquid fuel. The reaction is carried out
in an autoclave at temperatures of 480-750°F and pressures of
1400-4200 psia. Sodium carbonate is frequently used as a cata-
lyst for this reaction. However, the alkali salts present in
municipal refuse also can serve as the catalyst. A small scale
demonstration project is underway to evaluate the feasibility of
this process in Albany, Oregon.
The Worcester Polytechnic Institute process
converts municipal solid waste to a usable liquid fuel. In this
process, shredded refuse is slurried in paraffin oil and mixed
with a 0.2% nickel hydroxide catalyst. The slurry is pressur-
ized with hydrogen to 1000 psig in an autoclave and heated to
800°F. This hydrogenation reaction in the presence of a nickel
catalyst results in the production of oils (bitumens) from the
cellulose products in refuse. It does not appear that this
laboratory process is feasible for a full scale MSW treatment
facility.
3.4.2 Thermal Processes
Thermal decomposition of refuse in the absence
or partial absence of oxygen (pyrolysis) has been used for the
production of useful fuels. Solid, liquid, or gaseous fuels
can be obtained by a variety of pyrolysis processes. The
quantity of char, bitumen-like liquid, and gas produced varies
and is a function of the time-temperature sequence for each
particular process. At the present time the commercial pro-
cesses of four chemical companies have received considerable
attention: (1) Carborundum Company; (2) Monsanto Enviro-Chem
Systems; (3) Occidental Research Corporation; and (4) Union
Carbide.
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Monsanto Enviro-Chem Systems developed a pilot
process termed the Langard System which is being demonstrated in
a 1000 ton per day (TPD) facility in Baltimore, Maryland. (This
demonstration project has encountered a number of operational
problems)4. shredded refuse is partially burned with air in a
large rotary kiln. The products of this process are a low Btu
fuel gas (100 Btu/scf), a carbon char, and a glassy aggregate.
The ferrous metal is removed prior to combustion. The fuel gas
is burned in an afterburner to raise steam in a waste heat
boiler. The solid residue, which contains about 50% char, is
quenched and processed in a flotation separator. The char,
which is floated off the top of the cell, is landfilled and the
aggregate could be marketed as a roadfill material.
The Torrax process developed by the Carborundum
Company is a high temperature, air-fed slagging pyrolysis pro-
cess. This process converts refuse to a low heating value fuel
gas, char, and a fused frit. High process temperatures permit
fusion of the inert fraction of the refuse. Superheated air
introduced into the furnace supplies the thermal energy for
slagging of the noncombustibles. Natural gas or a fraction of
the pyrolysis gas can be used to preheat the air. The low
heating value of the pyrolysis gas (150 Btu/scf) requires that
it be used for steam generation in an adjacent boiler unit. The
carbon char recovered during the pyrolysis gas cleaning stage
can be reinjected into the gas at the boiler as a means of
increasing the heating value of the gas and improving the energy
recovery efficiency of the Torrax process. This process is
being evaluated in several European facilities.
Union Carbide's Purox system is another slagging
pyrolysis process. However, in this system oxygen is used in
place of air and the pyrolysis gas produced has a higher heating
value (300-375 Btu/scf). Although raw refuse can be directly
processed in the furnace, it is advantageous to coarsely shred
the refuse and remove the ferrous metal prior to pyrolysis.
Liquid and solid organics entrained in the pyrolysis gas are
removed and recycled back to the furnace to be decomposed. The
only products from the Purox system are the medium Btu fuel gas
and a glassy slag. A 200 TPD pilot facility is being studied in
South Charleston, West Virginia.
The Occidental Research Corporation has devel-
oped a short residence time, flash pyrolysis process which
converts finely shredded, air-classified refuse into a combus-
tible liquid, a medium Btu fuel gas and a char residue. The
char and fuel gas are recycled for use in the pyrolysis system.
The process is designed to maximize the liquid fuel yield. This
liquid fuel is a highly oxygenated acidic tar, which is somewhat
corrosive and viscous. A 200 TPD plant to demonstrate this pro-
cess has j.ust been completed in El Cajon (San Diego County),
California.
10
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In addition to the four major commercial pyro-
lysis processes described, there are other pilot and laboratory
processes that utilize a variety of existing and furnace designs
and produce a wide range of fuel products. Rotary kilns, verti-
cal and horizontal shaft furnaces, fluidized bed furnaces, and
a variety of batch type reactors have been employed for fuel
production. A number of these systems may reach commercial
status within the next several years.
3.5 Thermal Decomposition of Cellulose
An effective insight to the pyrolysis of municipal solid
waste can be obtained by studying the thermal decomposition of
cellulose and cellulose products. The pyrolysis of cellulose
can be viewed as a two stage process: (1) dehydration; and
(2) depolymerization, though there does not appear to be a
sharp delineation between the two. Below 390°F the predominant
reaction is dehydration. Water vapor and traces of carbon
dioxide, formic and acetic acids, and glyoxal are evolved.
Between 390°F and 535°F both dehydration and depolymerization
reactions occur. Larger quantities of carbon dioxide, formic
and acetic acids, and glyoxal are evolved at these temperatures.
In addition, small amounts of carbon monoxide may be released.
Above 535°F the primary pyrolysis reaction is depolymerization.
This is achieved by scissions of the C-0 bonds in the cellulose
chain, either in the rings or between rings. Scissions of C-0
in the rings result in the disintegration of the ring to yield
CC>2, CO and 1^0. Scissions of the C-0 bonds between rings
results in the production of levoglucosan molecules. Depending
on the reaction conditions levoglucosan may either volatilize
or decompose thermally to yield gases and a carbonaceous mate-
rial. The main volatile products from levoglucosan decomposi-
tion are CO, H2, CH4, C02, acetic acid, ethanol, acetaldehyde,
acetone, biacetyl, methylethyl ketone, ethylacetate, and tars.
Above 930°F secondary decomposition and gasification of the
char occur. A summary of the pyrolysis reactions for cellulosic
materials is presented in Table 4.
TABLE 4. PYROLYSIS REACTIONS OF CELLULOSE
Temp. (°F) Process Major Volatile Products
<390°F dehydration water vapor
390-535°F endothermic CO2, water vapor and
dry pyrolysis acetic acid
535-930°F exothermic CO, H2, CH4, CO2, acetic
pyrolysis to acid, ethanol, acetalde-
char hyde, acetone, biacetyl,
methylethyl ketone, and
tars
>930°F gasification HCHO, H2, and CO
of char
11
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As indicated, organic liquids, char, water, and a gas
are produced from the pyrolysis of cellulose. The quantities
generated are controlled by the heating rate, final temperature
and length of exposure to final temperature. In general, the
char will constitute between 20-40% of the final product mix,
the organic liquids and gas phase can vary between 10-40%, and
water constitutes the remaining fraction. The thermal process
employed can be designed to maximize the end products desired
from the cellulose wastes. Higher heating rates and higher
temperatures produce larger quantities of gas and less char.
Conversely, lower heating rates and lower temperature processes
result in increased char production.
The quantity of char, the composition of the gases and
liquids evolved, and the necessary reaction temperatures can be
significantly affected by the presence of chemical agents in the
cellulose materials. A number of chemical compositions have
been identified which increase the quantity of char produced
and decrease the amount of combustible gases and tars formed.
Many of these compounds were developed for flameproofing cellu-
losic materials.
In general, the flameproofing agents are selected to
direct the pyrolysis process toward maximum production of char,
minimum production of tars, and the highest possible propor-
tions of water and carbon dioxide. Over 400 chemicals have been
evaluated for use in flameproofing treatments of cellulosic
materials. The highly effective compositions are all soluble in
water, and most are salts of either strong acids or bases.
Strong acids encourage pyrolysis to carbon and water by their
reactivity with hydroxyl groups in the cellulose chain. Elimi-
nation of water by removal of hydroxyl and hydrogen atoms allows
the carbon atoms joined by a double bond to remain as a charcoal
residue. In addition, many oxidizing agents attack cellulose
and have been found to be effective fire retardants. Oxidized
cellulose pyrolyzes rapidly at lower temperatures giving high
charcoal residues.
A number of laboratory and pilot processes have been
developed to produce charcoal from cellulose wastes by pyroly-
sis. Except for the work of Dr. A. Harendza-Harinxma,5 there
is no reported use of chemical additives to promote the quantity
of char produced. In most of the processes reported in the
literature pyrolysis was carried out between 930-1650°F and the
char residue was about one-third to one-fourth of the product
mix. From 20-50% of the char residue was inert material, and
the char usually contained about 15% volatile materials.
12
-------
3.6 Biological Processes for Product Recovery
A number of anaerobic digestion processes have also been
developed for generating methane gas from solid organic wastes.
In many of these processes, municipal refuse and sewage sludge
can be combined in the digester. Maximum energy recovery is
less than 50% since over half the organics are not digestible.
This residue must be disposed of or used in some other type of
fuel recovery process.
A variety of chemical processes have also been devel-
oped for converting the organic portion of the refuse into other
useful products. Wet oxidation, hydrolysis, and photodegrada-
tion processes have been developed in the laboratory for pro-
ducing protein, glucose, alcohol, yeasts, and acids from solid
wastes. None of these processes has progressed to the full-
scale demonstration phase.
3.7 Some Current Problems
Although many of the laboratory, pilot, and full scale
projects have demonstrated the basic technical feasibility of
the various energy recovery systems, there are still a number
of problems in trying to utilize these processes for full scale
MSW processing. This has been particularly true for those
processes producing fuels derived from refuse. Problems in
materials handling, storage, and combustion have been encoun-
tered. Incomplete combustion, increased particulates in the
effluent, corrosion, and large fluctuations in heat content
have been reported in a number of the full scale demonstration
projects. The translation of laboratory and pilot technologies
to full size scale-up has also presented a number of difficul-
ties. Improved quality and greater consistency of product are
necessary if the waste-derived fuel is to be a marketable
product for large-scale usage.
13
-------
SECTION 4
LITERATURE SEARCH
A literature search was conducted to identify processes
for improving the quality of the products from the organic
fraction of municipal solid waste. In addition to seeking
more information about the conventional resource recovery
processes, processes for treating cellulose were also researched.
Mechanical, thermal, and chemical treatments used in cellulose
processing were of particular interest since cellulose is the
major constituent in the organic fraction. References con-
cerned with solid waste management and the wood, textile, pulp,
and paper industries were sought. An on-line literature search
of the following data bases were conducted:
1. CHEMICAL ABSTRACTS. Chemical Abstracts Condensates
covers the chemical literature from 1970 to the present and in-
cludes chemical engineering and chemical processes. Solid waste
treatment was reviewed as well as chemical processes for
cellulosic materials. Subject searching is available through
general subject section codes, title words, and assigned
descriptors.
2. COMPENDEX (Engineering Index). This data base
describes the engineering literature from 1970 to the present.
Engineering aspects of solid waste processing and engineering
processes concerned with cellulosic materials were covered.
3. NATIONAL TECHNICAL INFORMATION SERVICE (NTIS). This
data base covers Federal Government research and development
reports from 1964 to the present. All scientific and technical
disciplines are represented. Subject search capabilities are
provided by the Committee on Scientific and Technical
Information or COSATI Code, title words, and assigned descriptors
and identifiers.
4. SMITHSONIAN SCIENCE INFORMATION EXCHANGE (SSIE).
This data base contains information about recent and on-going
research. Approximately 2-year coverage is provided. Pro-
ject descriptions are maintained of Federal Government projects
covered by grants and contracts, many state and local govern-
ment projects, and university and foundation projects. All
scientific and technical disciplines are covered. Subject
14
-------
retrieval can be performed by title, abstract words, and
assigned subject terms.
5. SOLID WASTE INFORMATION RETRIEVAL SYSTEM. In
addition, the EPA Solid Waste Information Retrieval System was
searched for pertinent items from its data base.
As a result of these searches, over 1,000 citations
were obtained and screened to identify the pertinent references,
Those so identified were ordered for review. Several hundred
documents and patents were ordered. The documents received
were logged in and filed, according to subject area. The
bibliography of compiled references is presented in Appendix I.
15
-------
SECTION 5
CARBON CHAR PRODUCTION
Thermal decomposition of organic materials in the
absence or partial absence of oxygen (pyrolysis) is used to
produce solid, liquid, and gaseous fuels. The quantity and
composition of the carbon char, bitumen-like liquid, and gas
obtained varies with the nature of the organic starting mater-
ial and the time-temperature treatment. The chemistry of
cellulose pyrolysis provides a reasonable model for the pyrol-
ysis of refuse, since cellulose is the major organic consti-
tuent (75%) of the organic fraction.
Although a number of pyrolysis processes have been
developed to produce carbon char, our literature research only
found one process using chemical treatment to promote char
formation. In the patented process developed by Dr. A.
Harendza-Harinxma, sodium aluminate (Na2Al2O4) is used to promote
carbon formation at temperatures below 660°F, whereas in most
of the conventional pyrolysis processes reported in the
literature, pyrolysis is achieved with thermal treatments from
930°F to 1650°F. In addition, the char yield is reportedly
increased for the sodium aluminate process. The char residue
comprises 20-40% of the final product mix, and contains from
30-50% inert material originating from the paper and plastic
fillers and the fine glass, metal, and stone retained in the
raw solid waste. The char also contains about 15% volatiles.
5.1 Chemical Treatments for Char Production
For conventional pyrolysis, carbon char production is
maximized by using lower heating rates and lower temperatures
of pyrolysis. As reported by Stevenson, et al,° pyrolysis
at 950°F produced 32% char while at 1670°F only 25% char was
produced.
It has been observed that certain chemical treatments
prior to pyrolysis can promote char formation at lower pyroly-
sis temperatures. Many 'of the chemical salts used to inhibit
combustion in cellulose products (flame-retardants) serve to
promote char production during pyrolysis. The effective fire
retardants act chiefly by directing the decomposition of
cellulosic materials toward the formation of few tars and more
water and charcoal, and by initiating decomposition at lower
temperatures.
16
-------
A study of flame retardants by McGeehan and Maddock pro-
vides a description of the semidurable and durable treatments
for imparting flame retardance. In addition to the more elab-
orate permanent treatments, the authors describe nondurable
treatments which involve water-soluble materials and are gener-
ally among the least expensive in terms of chemical and appli-
cation cost.
To promote low temperature charring of municipal solid
waste, research should clearly be directed to the nondurable
chemical treatments because of their lower costs. A compilation
of potential chemical compounds for promoting char formation and
estimated quantities for treatment has been abstracted from the
McGeehan and Maddock paper, and is presented in Table 5. The
salts are usually combined and a synergism is often noted. For
example, boric acid alone is ineffective as a flame retardant,
but a mixture of 7 parts borax and 3 parts boric acid is effec-
tive at a ratio of 6.5 wt. per 100 wt. of fabric. This is
better than pure borax, which requires 60% by weight to be
effective.
As stated, salts that form acids or bases upon heating
are usually effective char promoters. Salts of strong acids
(chloride, bromide, iodide, sulfate, phosphate, etc.) and weak
bases such as ammonia are the most effective. One mode of
action for fire retardation is to increase the carbon residue
and decrease the loss of flammable gases and liquids. One
possible mechanism for this effect involves the well known
catalytic ability of strong acids in bringing about dehydration
of alcohols. Although dehydration formally involves loss of
hydroxide ion (OH~) from one carbon atom, and loss of hydrogen
ion (H+) from an adjacent carbon atom, such a reaction is quite
difficult due to the powerful basicity of the hydroxide ion.
Protonation of the hydroxyl group by an acid weakens the C-0
bond, and permits the departure of water, a much weaker base
than hydroxide ion.
H-
-------
TABLE 5. POTENTIAL CHAR PROMOTERS
00
wt.
Chemical 100 wt.
Ammonium Salts
Bromide
Molybdate [ (NH. ) 2Mo04 ]
Phosphate l(NH4)2 HPO4]
Iodide
Sulfate
Chloride
Borate (NH4BO3>
Sodium Salts
Tungs tate (Na2W04 - 2H20 )
Stannate (Na2Sn03)
Aluminate (Na2Al2O4 )
Silicate (Na2Si03-9H20)
Bisulfate (NaHSO4)
Arsenate (Na3As04- 12H2O)
Borate (Na2B407 • 10H2O
Miscellaneous
Phosphoric Acid
Zinc Chloride
Calcium Chloride (CaCl2.6H2O)
of chemical
of cellulose
7
7
12
14
18
22
24
9
18
19
20
30
33
60
12
12
14
moles
100 wt. of cellulose
0.071
0.036
0.091
0.097
0.14
0.41
0.31
0.027
0.085
0.23
0.25
0.16
0.12
0.064
Magnesium Chloride 16
-------
(high b.p.) or phosphoric acid, and ammonium phosphate (high
b.p.) is between the bromide and the chloride in effectiveness.
Obviously other factors such as acid strength, thermal stability
of the salt, and flame retardation effects not related to dehy-
dration (e.g., foaming and radical scavenging) must be consid-
ered to provide a quantitative explanation of effectiveness.
Calcium chloride is an effective retardant at the 14 wt.
percent level. While this may seem excessive compared to
several other salts, economics could make it a desirable reagent
for enhancing char formation. The Solvay process for making
soda ash (Na^COj) produces calcium chloride as a by-product.
Soda ash producers are permitted to dispose of CaCl2 in the
ocean, but not in fresh water. As a result, soda ash producers
lacking access to the sea have a disposal problem. If CaCl2
does serve effectively to increase charring at lower pyrolysis
temperatures, it could be the most feasible chemical salt for
use in treating refuse prior to pyrolysis treatment.
5.2 Laboratory Studies
During this project three char-promoting materials
(NH^Cl, CaCl2/ and Na2Al204) were coated on filter paper and
evaluated in a nitrogen atmosphere (to eliminate any effects due
to the presence of oxygen). Thermogravimetric analysis (TG),
was used to study the pyrolysis of these papers as a function
of the chemical treatment.
All of the chemical treatments initiate weight loss at
lower temperatures than with untreated paper. The NH^Cl treat-
ment appears to induce decomposition between 390°P ana 570°F,
and does not leave a residue as does the Na2Al2C>4, and CaCl2.
Interpretation of the resultant TG data was not by itself con-
clusive. Visual inspections of larger samples heated in a
nitrogen atmosphere were also conducted to better assess the
chemical treatment. The data from the TG for the three chemical
treatments are presented in Figure 1.
t
Untreated filter paper undergoes slight darkening at
383°F, and becomes brown at 430°F. Similarly, NH4Cl-treated
paper begins to darken at 300°F and is nearly black at 383°F.
The TG data are consistent with these observations.
In contrast, filter paper treated with CaCl2 failed to
show any darkening at 383°F, and is only slightly darkened by
428°F (the sample which had been heated to 383°F was brittle).
The TG data for CaCl2~treated paper did not readily relate to
the visual observations.
Other studies with CaCl2-treated newspaper were conduc-
ted concomitantly with the foregoing experiments. Some slight
19
-------
100
no treatment
0 212 392 572 752 932
Temp., °F
Figure 1. Results of Thermogravimetric Analysis in a
Nitrogen Atmosphere.
20
-------
char promotion was suggested by these results, but the effect
was deemed too slight to be of significance.
The results from these preliminary studies showed that
NH4C1 was a more desirable char promoter than CaCl2 anc^
Na^A^O.. The NH^Cl initiates the decomposition at lower tem-
peratures and does not remain as a salt residue at the comple-
tion of the process. It also may be possible to recover the
NH4C1 vapors for reuse.
5.3 Evaluation of the Process Developed by Dr. A. Harendza-
Harinxma
Dr. Harendza-Harinxma has developed a process to pyro-
lyze municipal refuse and sewage sludge to a char and fuel gas.
The essence of this concept is the use of sodium aluminate to
promote carbonization at low processing temperatures (480-570°F)
with an increased production of char. The general flow plan
proposed by Dr. Harendza-Harinxma is presented in Figure 2.
In this proposed process, sewage sludge is used as the
solvent for a 2-4% solution of sodium aluminate. This solution
is mixed with municipal refuse (two parts sludge to one part
refuse). According to the flow plan the refuse is to be
coarsely shredded, however, the metal and glass fraction need
not be removed prior to carbonization. (Nevertheless, it would
be desirable to remove the metal and glass prior to mixing the
refuse with the sludge to prevent excessive wear on the process-
ing equipment.) The slurry mixture is then mechanically de-
watered, resulting in a thickened sludge of 40-60% solids. This
sludge is thermally dried to about 15% moisture content. The
dried refuse-sludge mixture, impregnated with sodium aluminate,
is then carbonized for about one hour at 480-570°F.
The carbonization process takes place in a rotary kiln
and converts the dried waste to a char and a fuel gas. The
proposed rotary kiln consists of inner and outer cylinders with
a plenum between the two. The inner cylinder is divided into
five chambers, with the first, third, and fifth chambers con-
taining small round holes. The carbonized material tends to be
brittle and is pulverized during the rotation process. The
pulverized char falls through the openings in chambers three and
five and is collected at an exit port. The pyrolysis gases flow
up through the refuse-sludge mixture and exit through the small
openings in chamber one. The gas was reported by Dr. Harendza-
Harinxma to have the following average composition by weight:
H2, 2%; CH4, 2%; CO, 11%; C02, 70%, and N2, 15%. From 15,000 to
24,000 cubic feet of gas are produced per ton of refuse. The
char represents from 20-40% of the starting weight (400-800 Ibs/
ton MSW). According to data provided by Dr. Harendza-Harinxma,
the gas produced from a ton of refuse is calculated to have a
21
-------
MUNICIPAL
SOLID WASTE
COARSE
SHREDDER
o
MIXING
TANK
(PUG MILLl
MECHANICAL
DEWATERING
(CONE PRESS)
ROTARY DRYER
CARBONIZING
RETORT
(ROTARY KILN)
CHAR AND
SODIUM ALUMINATE
METAL AND GLASS
REMOVAL
(MAGNET & TROMMEL)
SODIUM
ALUMINATE
Figure 2. Basic Flow Plan for Harendza-Harinxma Process,
22
-------
heat content of 3.1 x 106 Btu (127 Btu/ft3) which would classify
it as a low Btu gas. The char produced contains about 30% inert
and about 15% volatile materials. A University of Dayton Re-
search Institute (UDRI) analysis of the char showed a carbon
content of 56% and a hydrogen content of 3.5%. The heat value
of the char ranged from 8,000 to 11,000 Btu/lb depending on the
specific composition. Samples of char measured at UDRI had an
average heat content of 10,000 Btu/lb. An analysis of the inert
fraction of the char residue is given in Table 6.
TABLE 6. ANALYSIS OF THE INERT FRACTION IN THE CARBON CHAR
Crystalline Compounds Identified
1. CaSi04 * H20
2. Na2Al204
3. Ca4Al6013 • 3H2O
4. Other possible phases -
-------
One possibility would be to use the Black Clawson wet
process for Dr. Harendza-Harinsma1s concept (Figure 3). In the
Black-Clawson process the refuse is pulped and the metal and
glass are removed by wet processing techniques. The organic
fraction is dewatered and the paper fiber can be recovered or
the entire fraction can be used as a fuel. This RDF fraction
(40-50% solids) could be mixed with a sewage sludge solution of
sodium aluminate and the slurry could then be mechanically de-
watered. This semidried (50% solids) material could then be
further dried thermally. The refuse and sludge impregnated with
sodium aluminate could be carbonized in a rotary kiln. The
resultant pyrolysis gas could be used for the thermal drying
process after it is cleaned. Using this general flow plan a
theoretical material and energy balance was developed and is
presented in Figure 4. A summary of the assumptions and calcu-
lations employed for this theoretical process is presented in
Table 7. All assumptions were based on the information fur-
nished by Dr. Harendza-Harinxma, laboratory results at the
University, and information from the pyrolysis literature. The
calculated efficiency for this process is approximately 44%.
5.4 The Market Potential for Carbon Char
As described, pyrolysis of municipal solid waste results
in the production of a solid residue (char) and a fuel gas. The
residue consists of a carbonaceous material from part of the
organics and inorganic fraction. A major concern is the market
potential for the char residue. If large quantities are to be
produced, then long term valid markets must be available.
A number of potential markets have been identified for
the char resulting from the pyrolysis process:
a. Solid fuel
b. Feed stock for preparing gaseous or liquid fuels
c. Substitute for the carbon now being used in carbon
and graphite products (activated carbon, charcoal, carbon fill-
ers, carbon risers, etc.)
As a solid fuel, the char would contain between 8,000 and
10,000 Btu/lb and could be a substitute for powdered coal in a
suspension fired boiler. The higher amount of inert material
(three times that of coal) and the volatile content (about one-
half that of coal) would be a drawback in its use as a fuel.
The price of coal varies from about $0.50 to $1.60 per million
Btu ($20 to $40/ton). However, it is unlikely that the char
could command an equivalent price with coal recognizing its
higher ash content, as well as the expected fluctuations in
chemical composition. It is estimated that about 1 ton of ref-
use would produce about one-third of a ton of char. Therefore,
per ton of refuse, one might hope to obtain from $3 to $6
24
-------
MUNICIPAL
SOLID WASTE
RECEIVING FLOOR
& STORAGE
ce
en
NON-MAGNETIC MATERIALS
HYDRAPULPER
JUNK
REMOVAL
LIQUID
CYCLONE
HEAVY
FRACTION
GLASS & METAL
RECOVERY
ORGANIC
REJECTS
THICKENING &
DEWATERING
BLACK-CLAWSON RDF
PROPOSED ALTERNATE PROCESS
MIXING TANK
MECHANICAL
DEWATERING
GAS CLEANING
*
ROTARY
DRYER
FUEL
GAS
CARBONIZATION
FURNACE
SEWAGE SLUDGE
SODIUM ALUM I NATE
CARBON CHAR
Figure 3. Modified Black-Clawson Wet Process,
25
-------
MSW
8.8 x 106 BTU
I
SEWAGE SLUDGE
5% SOLIDS
ORGANICS - 110*
INORGANICS - 90*
WATER - 3800
1.6 x 106 BTU
"1
PROCESS WATER
1
BLACK-CLAWSON
WET PROCESS
PROCESSED MSW
18% SOLIDS
ORGANICS - 8611
INORGANICS - 81*
WATER - 4166*
x
* <
*
MIXING TANK
13% SOLIDS
INORGANICS
SODIUM ALUMINATE
8M
SLURRY 6460*
1% SOLIDS (50*1
SOLIDS - 12221
WATER - 79661
MECHANICAL I ELECTRICAL REQUIREMENTS
1,228.320 BTU
WATER - 15561
SOLIDS - 1172*
ORGANICS - 944*
INORGANICS - 228*
1426*
WATER VAPOR
ROTARY DRYER
212°F
^ 2,244,761 BTU
FOR DRYING
1696* AT 1B2°F
ORGANICS - 944
INORGANICS - 228
WATER - 130
AIR - 394*
ROTARY KILN
FOR
CARBONIZATION
662°F
654,355 BTU
FOR CARBONIZATION PROCESSES
PYROLYSIS GAS
1111.5*, 23, 100 FT3
AT200°F
481* C02 (49»>
112* CO 110*1
139* H20 (12.5)
301* N2 (27V
40* HEAVY HYDROCARBONS (4»>
11* CH4 (1%)
26* H2 12%)
1.5*CL& S (1.%)
3,138,133 BTU
Figure 4. Material and Energy Balance.
26
-------
TABLE 7. MATERIAL AND ENERGY BALANCE CALCULATION FOR
ONE TON OF MUNICIPAL SOLID WASTE
I. Proposed Average Composition for MSW
A. Organic Fraction
Paper - 40%
Other Organics - 37%
B. Inorganic Fraction
Metal - 11%
Glass - 8.5%
Inerts - 3.5%
(moisture - 30%)
II. Composition of the Organic Fraction from the Black-Clawson
Process for 1 ton MSW°
Organic Material - 861 Ibs
Noncombustibles - 81 Ibs
Water - 4,166 Ibs
III. Composition of Sewage Sludge (5% Solids) and Sodium
Aluminate
Organics - 110 Ibs
Noncombustibles - 90 Ibs
Sodium Aluminate - 80 Ibs
Water - 3,800 Ibs
IV. Heat Content
A. MSW as received - 4,400 Btu/lb x 2,000 Ibs/ton =
8.8 M Btu
B. Sewage Sludge (5% solids) - 8,000 Btu/lb solids x
200 Ibs = 1.6 M Btu
C. Total Heat Content of Wastes
8.8 M Btu
+ 1.6 M Btu
10.4 M Btu
V. Estimated Energy Requirements for MSW Processing and
Blending MSW, Sludge, and Sodium Aluminate
Operation of all mechanical and electrical equipment -
120 KWH
Assuming an efficiency of 33% for the generation of
electric energy gives:
x 3412 = 1,241,000 Btu = 1.24 M Btu
27
-------
TABLE 7. MATERIAL AND ENERGY BALANCE CALCULATION FOR
ONE TON OF MUNICIPAL SOLID WASTE (Continued)
VI. Composition in Mixing Tank '
Organics - 971 Ibs
Inorganics - 251 Ibs
Water - 7,966 Ibs = 9,188 Ibs/ton MSW
VII. After Mechanical Dewatering
Solids - 1,172 Ibs
Water - 1,556 Ibs
VIII. Drying
A. Material Balance
IX.
Composition Quantity (M)
Organics
Inorganics
Water
944 Ibs
228 Ibs
1,556 Ibs
Specific
Heat (Cp)
Btu/lb/°F
0.3
0.2
1.0
Latent
Heat (L)
Btu/lb
970
B.
Thermal Requirements: To Heat the Waste in a Dryer
from 60°F to 212°F (AT = 152°F)
M x Cp x AT = Btu
Organics
Inorganics
Water
Water Vaporization
944 x 0
228 x 0
1,556 x 1
1,556 x 970
3 x 152
2 x 152
0 x 159
TOTAL
43,046
6,931
236,512
1,509,320
1,795,809 Btu
Allowances for heat losses - 25%
.*. 1,795,809 x 0.25 = 448,952
Total heat requirement for drying
1,795,809
448,952
2,244,761 Btu
* 2.24 M Btu
Carbonization
A. Composition to Rotary Kiln
Organics - 944 Ibs
Inorganics - 228 Ibs
Water - 130 Ibs
Entrapped Air - 394 Ibs
28
-------
TABLE 7- MATERIAL AND ENERGY BALANCE CALCULATION FOR
ONE TON OF MUNICIPAL SOLID WASTE (Continued)
B.
D.
H.
Proposed Chemical Composition for Feed to Carbonization
Kiln
C 0 H N Cl S Total
Organics 472 405
Inerts
Air 99 295 394
Water 116 14 130
57
944
472 620 71 301
1 1,696
209,004 Btu
Thermal Gradient AT from 182°F (out of dryer) to 662°F
(for carbonization) = 480°F
Sensible Heat
M x Cp x AT
Organics 944 x 0.3 x 480 = 135,936
Inorganics 228 x 0.2 x 480 = 21,888
Water 394 x 0.25 x 480 = 47,280
Water Vaporization 130 x 1.0 x 30 = 3,900
TOTAL
Water Vaporization
130 x 970 = 126,100 Btu
Sensible Heat for Water Vapor
130 x 0.475 x 450 = 27,788 Btu
Carbonization Energy
291,463 Btu
Total Heat Requirements for Carbonization
Sensible Heat
Vaporization
Heat for Water Vapor
Carbonization Energy
209,004
126,100
27,788
291,463
654,355 Btu
Carbonization Products - Carbon Char and Pyrolysis Gas
1.
Carbon
C
O
H
Cl
S
Inerts
- 270 Ibs (46%)
- 61 Ibs (10%)
- 23 Ibs ( 4%)
2 Ibs (0.3%)
- 0.5 Ibs (0.1%)
- 228 Ibs (39%)
584.5 Ibs
29
-------
TABLE 7. MATERIAL AND ENERGY BALANCE CALCULATION FOR
ONE TON OF MUNICIPAL SOLID WASTE (Continued)
2.
3.
Pyrolysis Gas
C 0
H
N
Cl
Total (Ibs)
H2O
CnHn^n
CH4
ti o
C1 - t G
J-^oc a
TOTALS
AQ
16
8
202
7 Kl
JJJ.
123
21
559
16
3
3
48
301
301
:::
l
—
—
Oc
. D
0.5
139
301
40
11
1C
. 3
1111.5
Ibs
The compositions proposed for the char and pyrolysis
gas are based on the data from the literature,
information obtained from Dr. Harendza-Harinxma and
observations from University of Dayton laboratory
studies.
Estimated Heat Content of Pyrolysis Products
a. Carbon Char (9,500 Btu/lb)
9,500 Btu/lb x 584.5 Ibs = 5,552,750 Btu
In addition, the heat contained in the hot char
exiting the kiln may also be recovered. For this
calculation a specific heat of 0.175 and a AT of
400°F is assumed:
584.5 x 0.175 x 400 = 40,915 Btu
Total heat content of char = 5,593,665 Btu
* 5.59 M Btu
Pyrolysis Gas*
CO - 112 Ibs
H2 - 26 Ibs
CH4 - 11 Ibs
CnH^Or, - 40 IbS
x 4,347 Btu/lb =
x 61,100 Btu/lb = 1,
x 23,879 Btu/lb =
x 20,000 Btu/lb =
486,864
588 ,-600
262,669
800,000
3,138,133 Btu
3.14 M Btu
X.
Energy Balance
Estimated Energy Content from 1 Ton MSW and 200 Ibs of
Sewage Sludge = 10.4 M Btu
Estimated Energy Requirements to Process MSW and Sludges:
Mechanical and Electrical Equipment 1.23 M Btu
Drying
Carbonization
2.24 M Btu
0.65 M Btu
Energy Content of Pyrolysis Products
5.59 M Btu + 3.14 M Btu = 8.73 M Btu
4.12 M Btu
30
-------
TABLE 7. MATERIAL AND ENERGY BALANCE CALCULATION FOR
ONE TON OF MUNICIPAL SOLID WASTE (Concluded)
Estimated Energy Efficiency
(8.73 - 4.12) M Btu
10.4 M Btu
x 100 = 44%
MSW + Sludge_
I0.4M BTU
Pyrolysis
Process
8.73M BTU Net Energy _
Process Output
[ Energy for Process
4.6IM BTU
4.I2M BTU
31
-------
in revenues for the sale of char as a solid fuel. Representa-
tives from the Dayton Power and Light Company have expressed
reservations about the acceptability of the char as a fuel.
They felt that its low volatility would make it difficult to
burn and the high ash content could be a problem. In addition
the fusion temperature of the ash must be above 2550°F to mini-
mize slagging.
The char residue could also be used to replace coal as
a feedstock for the generation of synthetic liquid or gaseous
fuels. Although coal has a market value of $20-$40/ton, char
with a carbon -content of 50% to 60% (versus 75% for coal) could
not command identical market value. In addition, its large
inert fraction and somewhat lower hydrogen content (three-
fourths that of coal) further reduces its economic potential.
Another potential use for char is as a raw material for
carbon and graphite products. Carbon is used for filtration,
in the production of electrodes and brushes, for refractory
ware, in the production of iron and steel, in the production of
rubber and plastic products, in charcoal, and in asphalt prod-
ucts. Inquiries were made regarding the potential market for
the char to the following firms:
ARMCO Steel Ohio Rubber
Union Carbide Premier Rubber
Dayton Walther Akron Chemical
Inland Manufacturing SOHIO
ALCOA Great Lakes Carbon
Dayton Tire and Rubber
Their assessment of the market potential for the carbon char
assumed the generalized composition of the material provided by
Dr. Harendza-Harinxma.
The carbon char from pyrolyzing solid waste can be acti-
vated and used for waste water filtration treatment. In studies
by Stanford University^ it was found that the activated char
from MSW pyrolysis had comparable adsorptive properties to
commercial carbons for COD (chemical oxygen demand) removal in
water samples. Preliminary cost analysis showed that the use
of char was competitive with commercial carbon products. A
more intensive study of the technical and economic factors is
in progress. In addition, a market analysis is planned to
determine the realistic potential and level of demand for the
carbon char as an activated carbon. (Private communication,
Dr. J.O. Leckie, Stanford, University.)
Discussions with other sources have indicated two
problems with the activated carbon from pyrolyzed refuse:
32
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a. Chemical quality
b. Limited potential demand
Representatives from the carbon industry felt that the carbon
char might not satisfy the rigid chemical specifications.
Soluble metal content and anticipated fluctuations of chemical
composition were the two areas frequently mentioned. The second
problem, potential market size, was also raised several times.
At the present time the number of tertiary sewage treatment
plants is limited, and the demand for activated carbon is small.
A plant processing 1000 tons of refuse per day would generate
300 tons of activated carbon per day.
Another possible application for the carbon char is as a
raw material for the manufacture of carbon brushes and consum-
able electrodes. The carbon char could serve as a partial sub-
stitute for the petroleum coke now used in these applications.
Some motor brushes contain a mixture of carbon and abrasives.
It is felt that the inert fraction in the carbon char could
function as the abrasive. However, the lower carbon content,
the varying composition and higher volatile content were found
to be objectionable. The quantity of carbon used for this
application was not known, however, it was felt that the carbon
char would only be acceptable as a partial substitute in the raw
material blend.
The aluminum industry uses large quantities of carbon for
consumable electrodes in the arc melting process. About one
million tons of calcined petroleum coke are used annually. The
current price for high quality petroleum coke is $100/ton
($0.05/lb). However, the rigid specifications for these elec-
trodes, especially the silicon, iron, and ash content would ex-
clude the char from consideration;
SPECIFICATIONS FOR ALUMINUM ELECTRODES
Property
Volatiles ,
Silicon
Iron
Vanadium
Sulfur
Moisture
Fixed Carbon
Weight (%)
0.5
0.02
0.03
0.01 to 0.
0.02 to 0.
0.5
0.75 to 0.
04
04
85
Particle Size Minus 1 inch plus 100
mesh 3
Density 2.05 gin/cm
33
-------
The feasibility of using the char as a raw material for
the manufacture of carbon and graphite crucibles and other
refractory ware was also explored. Based on the established
specifications for these products, the char does not appear to
be an appropriate raw material. The feasibility of using the
char for producing calcium carbide for the production of acety-
lene was also investigated. Based on information from the Union
Carbide Corporation, it would also appear that this would not be
a feasible application for the char.
The use of the char as carbon risers in the production of
steel and high carbon iron was also investigated. Carbon and
graphite pellets are added to the steel and iron melts to raise
the carbon content. Two to three pounds of carbon are used per
ton of steel. About 100 million tons of steel are produced
annually (requiring approximately 150,000 tons of carbon).
About 30 to 40 Ibs of carbon are used per ton of gray iron. The
requirements for the carbon specify less than 0.5 percent sulfur
and high density. Consequently, the carbon char would have to
be densified into 1/8-inch diameter pellets. In addition, the
rate of solution of the char in the ferrous melt would have to
be established by laboratory tests. It appears that the carbon
char could be an acceptable substitute for this application.
The iron and steel industry presently pays about $0.05/lb for
scrap carbon and graphite which contain about 85% carbon.
Another application considered for the carbon char is in
the production of rubber and plastic products. At the present
time, about 3 billion Ibs of carbon black are produced annually.
About 93% is used in rubber products to provide reinforcement
and abrasion resistance and the remaining 7% is used in plastics,
paints, and ink. About 75% of the rubber products are used in the
automotive industry, with more than half being used in the pro-
duction of automotive tires.
The majority of carbon black is made from petroleum
derivatives, and the small remainder is made from natural gas.
The present cost of carbon black is about $0.15/lb and all in-
dications are that the price will be increasing. The specifica-
tions for the carbon black used in tires are very rigid and it
does not appear that the char could be considered. However, in
nonstructural rubber products the specifications are not so
restrictive and the char might well qualify. The major require-
ment would be particle size which would necessitate grinding and
screening the char.
Discussions with rubber producers indicated that they
might accept a carbon char of proper particle size if the cost
were $0.03-$0.05/lb. Nationwide it is estimated that 500,000
tons of carbon black are used in nonstructural rubber products.
However, no single plant would require more than 10,000 to
34
-------
20,000 tons of carbon a year. The costs of transportation, as
well as further processing of the carbon char, would be impor-
tant factors to consider in determining its applicability in
nonstructural rubber products.
Charcoal briquettes represent another potential applica-
tion for the use of the carbon char. Each year some 750,000
tons of briquettes are produced. An average sized plant will
produce 40,000-50,000 tons per year. The current market price
for raw carbon for briquetting ranges between $40 and $60 per
ton with an average of about $50 (2.5 cents/lb). According to
a representative from the Great Lakes Carbon Corporation, the
charcoal normally used for briquettes contains about 75% carbon
and has about 15% inorganic ash. If the ash content is too high
(above 24%), the briquettes exhibit poor burning characteristics.
The lower carbon content (50-60%) and higher ash content (30-
50%) of the char from MSW would make this material less desir-
able, however, it could be used as a partial constituent in the
manufacture of charcoal briquettes. It was estimated that the
char from MSW could be used for about half of the briquette
composition if the price were favorable (1.5 to 2 cents/lb). Based
on current estimates a ton of refuse could generate about $9.00
worth of char.
A plant processing 1000 tons of refuse per day could
generate up to 300 tons of char per day or about 79,500 tons
per year. If the MSW char supplied about half of the material
for the briquette production, a single MSW processing facility
could supply about four average sized charcoal plants. Based
on current projections it would appear that the entire charcoal
briquette market would support only 4 or 5 refuse processing
facilities. The potential market for the char as an ingredient
in charcoal briquettes was determined in a telephone interview;
however, a detailed analysis of the char by charcoal manufac-
turers would be necessary to more accurately define its market.
A final application considered for the char was in as-
phalt and asphalt products. As a partial replacement for the
asphalt, the char would have a very large market potential.
However, as a filler in asphalt products it would represent a
very small potential market for the char. Based on a prelimi-
nary assessment of the char by SOHIO, there is considerable
question about its acceptability for use in asphalt paving.
The current market value for asphalt is about $75/ton (4 cents/
Ib). If the char could be used for this application it is
estimated that the char would have a value of 1 to 2 cents/lb.
In summary, several potential applications have been
identified for the char. However, all of the identified appli-
cations are confronted with certain barriers. The major prob-
lems are the anticipated fluctuations in chemical composition
35
-------
and the high quantity of inerts in the char. Its low carbon
content relative to coal (56% vs. 75-85%) also reduces the mar-
ket value of the char residue.
It appears that the char can be used as a solid fuel and
as feed stock for synthetic liquid and gaseous fuels at a market
value of about $0.01/lb. With some additional processing the
char could also be utilized as an activated carbon, a raw mate-
rial for charcoal briquettes, a carbon riser in iron and steel
production and as fill in nonstructural rubber products at a
market value of $0.02-$0.04/lb. The major questions regarding
these latter applications concern the availability of sufficient
market demand. A plant processing 1000 tons of refuse per day
could more than saturate many of the potential market opportu-
nities identified (79,500 tons/year). It is, therefore, very
apparent that each specific char-producing plant built must
secure a certified market for its product from one of the appli-
cations identified.
5.5 Engineering Analysis of a Plant to Convert MSW to a
Carbon Char
A preliminary engineering study of a plant to produce
carbon char from MSW and sewage sludge was conducted. Based on
the information accumulated, a design for a low temperature
pyrolysis facility was developed. The proposed facility would
process 1000 tons per 20 hour day (50 TPH) for six days per
week. The basic design for this plant is based on the Black-
Clawson wet processing system at Franklin, Ohio. The process
flow essentially follows the Black-Clawson process to dewatering
at the hydrodenser. After partial dewatering at the hydroden-
ser, the slurried refuse would be mixed with sodium aluminate
and sewage sludge in a flash mixer. This slurry mixture is then
mechanically dewatered in a* cone press and dried in a rotary
dryer. The dried refuse would then be pyrolyzed in a rotary
carbonization kiln. A flow plan and material balance for the
proposed plant is presented in Figure 5. The calculations
developed for the material balance at each step of the process
are presented in Table 8. The data used for the flow plan and
material balance were obtained from:
a. System Technology Corporation Report evaluating the
wet processing system8
b. U.S. Patent No. 3,961,025 Dr. A. Harendza-Harinxma
c. UDRI Laboratory Studies
The calculations developed served as a basis for determining
equipment sizes and operating requirements (flow rates, etc.).
This information was used to develop the environmental consid-
erations and to conduct an economic analysis for the proposed
plant.
36
-------
to
TIRES, f ^^
WHITT nnnn*: f \ . -
TREE STUMPS [UNPROCESSABLE] JUNK **
LOGS V WASTE / KtMOVAL
^^^~T**^^ ° *" a §
£ £ £ S! ^ £ MA
£ s a s 2 > w/
fe - ° 5401
1000 TPD TIPPING 942.5 *™™'l'uu'tl< ^
' FLOOR TPD ' Y.1* SOLIDS
RAW REFUSE
ORGANICS - 519 z
METALS - 80 o g
GLASS - 68 *- <
INERTS - 33 I S S
MOISTURE - 300 g"SS
WATER FROM WHITE """J^N
SEWAGE TREATMENT" * WAIbK ' \2 IS
PLANT
/LANDFILL\
V (FINES) y
/^ FERROUS \
I MtlAL r*
V 39. 1 TPD/
.5 TPD MAGNETIC
' SEPARAflON ""
KE-UP1 ^
UER fv si
3 TPD) N^
787 9 1 UQUID
J CYCLOMf
26, 187. 9 TPD
So
a
WATER HEA
0 TPD OEWA1
i
o
a.
VIES
FERING
g
203.6 TPD
CRUSHER
/FERROUsN
\H,7 TPD/
t/i Xm,^ ^^r
0
a:
UJ
u_
SURGE 13, 706.2 TPD
13,706.2 TPD
ALUMINATE ^-J-
TANK
3D
a.
HYDRO- 2506.2 TPD MIXING
(DEWATERING)
11,200 TPO
DRAIN WATER
( 25. 000. 000
FT3 PER DAY
COMBUSTION GAS
GAS
CLEANING
o
a_
i—
21,000,OOOFT3/D S
COMBUSTION GAS
4,000,OOOFT3/D
200 TPD
1/2 INCH A'"
SCREEN STORAGE
a
a.
i—
iTt
FLOAT
bLPAKAIION ' '
47.4 TPD
CARBONIZATION
KILN 650. (
662°F ' DR
850.6 TPD WA
\
/CARBON CHAR\
1 295 TPD 1
V(10.000 BTU/»I/
FLOAT FRACTION
IORGANICS)
SEWAGE
r- TREATMENT
PLANT
o " o
lig
t/> l/l
*
4,593.6 TPD
"• 13* SOLIDS Q
1
t—
O
n
MECHANICAL
DEWATERING '
o
a.
s
COMBUSTION
e
&
z
a;
o
1
THERMAL GAS PRODUCTS
TPD DRYER EVAPORATED
ED 2U f MOISTURE
STE 713 TPD
COMBUSTION
GAS PRODUCTS
Figure 5. Flow Plan for a Plant to Convert MSW to a Carbon Char.
-------
TABLE 8
MATERIAL BALANCE CALCULATIONS FOR A CARBON CHAR PRODUCTION PROCESS
Components
Refuse
Organics
Metal
Glass
Inerts
Moisture
Process Hater
Hake up water
Sewage Sludge
Organics
Inorganics
Hater
Starting
Composition - TPD
1,000
519
80
68
33
300
20,000
5,400
2,000
55
45
1,900
Unprocessable
Haste
57.5
42.5
10
5.0
To
Hydra
Pulper
942.5
476.5
70
68
33
295.0
20.000
To
Junk
Removal
124.6
30.3
60.1
10.8
9.4
14.0
30
Ferrous
Fraction
52.7
2.5
48.2
2.0
Nonferrous
Fraction
71.9
27.8
11.9
10.8
9.4
12.0
TO
Liquid
Cyclone
IU7.9
446.2
9.9
57.2
23.6
281.0
19.970
5,400
_« —
To
Heavier:
Dewatering
111.7
15.9
9.8
57.0
23.0
6.0
6,970
5,400
«•« v
Sodium Muminate
40
-------
TABLE 8 (Continued)
VO
Through
Crusher to
Components 1/2" screen
Refuse
organics
Metals
Glass
Inerts
Moisture
Process Hater
Make up Hater
Sewage Sludge
Organics
Inorganics
Hater
183.6
43.7
21.7
67.8
32.4
18.0
20
Residue
Fines
107.1
10.0
1.7
65.0
20.4
10.0
10
TO
Float
Separation
76.5
33.7
20.0
2.8
12.0
8.0
10
Nonferrous To
Metal Surge
Recovered Tank
34.1
3.7
18.0
1.4
6.0
5.0
5
706.2
430.3
0.1
0.2
0.6
275.0
13,000
From To
Mechanical Mixing
Dewater Tank
706.2
430.3
0.1
0.2
0.6
275.0
1,800
748.6
460.3
2.1
1.6
6.6
278.0
l.ROS
2,000
55
45
1.900
From
Mechanical
Dewatering
735.6
447.3
2.1
1.6
6.6
278.0
250
348
54
44
250
From
Thermal
Drying
522.
447.
2.
1.
6.
65.
98
54
44
6
3
1
6
6
0
Sodium Aluminate
40
30
30
-------
5.5.1 Environmental Considerations
The proposed low temperature pyrolysis plant
should result in significant reduction in solid waste (refuse)
and sewage sludge that would have to be landfilled or inciner-
ated. In addition, the materials recovered in the process could
reduce the need for an equivalent quantity of virgin natural
resources. Although the carbonization process should reduce
land pollution, it can contribute to the air and water pollu-
tion. Potential pollution problems and control technologies
associated with the proposed carbonization process have been
considered. The areas of major concern are discussed in the
following paragraphs.
5.5.1.1 Air Quality
The Clean Air Act Amendments of 1977
were signed into law by President Carter on August 7, 1977.
Certain aspects of these amendments could directly apply to a
carbon char plant. For example, for those areas which have not
attained ambient standards, so-called "nonattainment areas,"
states must have an approved implementation plan revision by
July 1, 1979, which provides for attainment of primary stan-
dards by December 31, 1982. This requirement is a precondition
for construction or modification of major emission sources in
non-attainment areas after June 30, 1979. Further, in both
"nonattainment" and "nondegradation" (those cleaner than ambient
standards) areas, major stationary sources may be constructed
only by permit, and must, at the very least, meet new source
performance standards prescribed by the law. Two sources of
possible air pollution have been identified for the proposed
pyrolysis facility: the combustion products from the dryer and
carbonization kiln, and the water vapor and dust from the dryer.
It is anticipated that the combustion products from burning the
fuel gas of pyrolysis would not present any serious problems
requiring environmental control equipment. The major products
should be H20, C02 and N2- In addition, minor amounts of NOX,
HC1 and S02 may also be present as well as some unburned hydro-
carbons. It is anticipated that there will not be any signifi-
cant quantity of heavy metals in the exhaust gases, since they
are more likely to be in the carbon char. One potential source
of air pollution is likely to be the dust entrained with the
water vapor driven off during drying. Dust control equipment
will probably be required for cleaning the water vapor before it
can be released to the atmosphere. A filter type unit or some
other type of dry dust collection system is envisioned. The
dust collected would be recycled back to the carbonization kiln
for processing.
40
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5.5.1.2 Water Quality
The proposed pyrolysis process for char
production is basically a wet process requiring large quantities
of water. Most of the water to be used would be obtained from
the nearby sewage treatment plant which would also supply the
sewage sludge. Most of the water used for processing would be
recycled, however, about 15 percent of the process water would
be returned to the sewage treatment plant each cycle and up to
5% is evaporated during the drying process. The waste water
returned to the sewage treatment plant is primarily from the
last mechanical dewatering step before drying. Based on the
data from an analysis of the Franklin, Ohio plant it is reason-
able to expect the waste water to have considerable suspended
solids and BOD loading. Estimates from the Franklin, Ohio
facility indicate a BOD loading of 100 Ibs BOD/ton refuse and
suspended solids loading of 160 Ibs/ton refuse. In addition,
considerable concentrations of heavy metals can also be expected.
At the Franklin, Ohio facility, total metal content of the waste
water (both suspended and dissolved) was found to be higher than
encountered in normal domestic waste water or landfill leachates.
It is evident that adequate precautions for treatment of the
water from the pyrolysis facility will have to be taken at the
waste water plant.
5.5.1.3 Bacteriological Considerations
There are likely to be bacteriological
hazards present at all solid waste and sewage treatment facili-
ties. It would appear that the problems at the proposed pyrol-
ysis facility would not be any different than that found at any
sewage treatment plant and airborne contaminants might be less
in a wet processing system.
5.5.2 Economic Considerations
A preliminary economic analysis was prepared for
the proposed pyrolysis plant. This analysis is based on the
process flow plan shown in Figure 5. The proposed plant would
have two processing lines each with a capacity of 25 tons per
hour for a total capacity of 1,000 tons of refuse per day. It
is assumed that the facility would operate 20 hours per day, 6
days per week for 52 weeks per year processing 265,200 tons of
refuse annually [1000 x 6 x 52 x 0,85 (on-line availability)].
It is further assumed that an adjacent landfill would serve as a
backup to the pyrolysis facility. Revenues for the facility
would be provided from several sources:
a) a tipping fee
b) sludge disposal
c) sale of aluminum and iron
d) sale of carbon char
41
-------
This preliminary economic analysis followed the format published
in EPA document SW-1579'10. A summary of the calculations
developed for the capital and operating costs are presented in
Table 9 and 10 respectively. Consideration of possible revenues
are presented in Table 11. The data presented in these tables
show an estimated total operating cost of $26.68/throughput ton
of MSW and a potential revenue of $17.15/throughput ton of MSW
plus revenue from sale of carbon char. For the pyrolysis facil-
ity to operate profitably the carbon char would have to sell for
$0.017 per pound ($34/ton) in order to cover the $9.53 deficit
calculated between total operating cost and identified potential
revenues.
TABLE 9. ESTIMATED CAPITAL COSTS (1977 Dollars)
Land (30 Acres at $10,000/acre) 300,000
Site preparation (35% of land cost) 105,000
Equipment, installation and facility construction 18,560,000
Engineering and Design (6% of 18,965,000) 1,138,000
Contingencies (10% of 20,103,000) 2,010,000
Start up and work capital 500,000
SUBTOTAL 22,613,000
Legal and financial costs (2%) 452,000
TOTAL PLANT COST 23,065,000
Municipal revenue bonds for project
(financing costs raise bond requirements
12% above capital cost of facility) 25,833,000
Estimate life of facility - 20 years
TOTAL INTEREST TO BE PAID (8%) 26,397,655
TOTAL CAPITAL COST 52,230,655
ANNUAL CAPITAL COST 2,611,533
ANNUAL THROUGHPUT (tons) 265,200
Capital Cost per ton 9.85
TABLE 10. ESTIMATED ANNUAL OPERATING &
MAINTENANCE COSTS (1977 Dollars)
Salaries & Benefits 923,000
Fuel 75,000
Electricity 963,000
Water & Sewer 111,000
Maintenance 696,000
Residue Removal 190,000
Materials & Supplies 1,070,000
Taxes (.75%) 173,000
Insurance & Management Costs ($1.00/ton) 265,000
Total Annual Operating & Maintenance Costs 4,463,000
Operating & Maintenance Cost per ton 16.83
42
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TABLE 11. POTENTIAL REVENUE SOURCES
Revenue Source Dollars/throughput ton
Tipping fee $ 8.50/ton
Sludge disposal (200 Ibs @ $50/ton) 5.00/ton
Ferrous metal (58 TPD at a net cost of 1.31/ton
$22.55/ton)
Stock for aluminum recovery 18 TPD 2.34
@ net cost of $130/ton
Sub Total 17.15
Carbon Char (295 TPD market values not
established) ?
5.6 Conclusions
The use of chemical treatments to promote carbon char
formation at lower pyrolysis temperatures has potential if a
reliable market for the char is secured. Laboratory results
clearly demonstrated that several chemical treatments can be
employed to generate char by low temperature pyrolysis. Both
sodium aluminate and ammonium chloride showed promise as char
promoters. An analysis of the projected economics for a low
temperature pyrolysis process reveals that a market providing
about $0.017 per pound for the char is necessary to make the
process economically viable.
Another major reservation concerning the use of the car-
bon char is the lack of user familiarity with it as a product.
Potential consumers are hesitant to commit themselves to an
untried material. To date, the commercialization of char gen-
erated from conventional pyrolysis processes has been rather
disappointing and this serves to moderate enthusiasm for a low
temperature pyrolysis process designed to produce a carbon char
product.
43
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SECTION 6
POWDERED SOLID FUEL
The conversion of the organic fraction of municipal
solid waste into a fine powder offers a number of advantages for
using this material as a solid fuel. A number of thermal and
chemical treatments have been identified that promote the con-
version of the organic fraction in refuse to a fine powder.
Most of these processes embrittle or degrade the cellulose
wastes.
6.1 Embritt lenient Studies
As part of this project, various chemicals were
screened for their ability to embrittle paper. Prospective
reagents that would be effective in the presence of the ambient
moisture (approximately 25% of the weight of solid waste) were
selected. It was felt that the ambient water may function as a
coreactant with the cellulose and the reagent in question, or
might serve simply as a solvent to concentrate the reagent on
the cellulose surface. Other desirable properties of the ideal
reagent include ease of application, recovery, reuse, and either
minimum retention in the final product or, if retained, a negli-
gible adverse effect on its utility. Gaseous reagents appeared
most likely to meet our criteria.
In the presence of water, one obvious reaction to
employ for degrading paper is acid-catalyzed hydrolysis. A great
deal of bonding between fibers in wood pulp papers may be due to
the action of hemicelluloses. To the extent that the hemi-
celluloses and cellulose are accessible to the aqueous acid,
hydrolysis should be effective in reducing the structural integ-
rity of the cellulosic material. However, workers at the Forest
Product Laboratories have reported little advantage in treating
wood with H2SO4 or HC1 prior to milling during the preparation
of microcrystalline cellulose. (Private Communication, June,
1977.) Hence, there appears to be a practical limit to the
extent of hydrolytic degradation of wood. (Of course it would
be pointless to strive for such finely divided material from
refuse.)
Embrittlement of paper via the formation of bonds be-
tween cellulose chains (crosslinking) appeared to be another
attractive possibility. The 50% decrease in the fold-strength
44
-------
of paper which has been heated at 350°F for 2 to 3 days is
thought to be partially due to this type of mechanism. Treat-
ment of paper with bidentate reagents capable of promoting
crosslinking under less demanding conditions therefore seemed
appropriate.
At the very outset of these screening studies it was
realized that the shredded newsprint selected was too dry and
homogeneous to serve as a model for municipal solid waste. For
many of the test runs we found it desirable to spray the paper
sample with water or a liquid reagent. The spraying process was
facilitated by the reactor described in the following paragraph.
Later experiments with a second type of paper (computer paper)
supplemented the initial studies with newsprint.
The experimental arrangement used in these studies is
shown in Figure 6. A three-liter, round-bottom reactor flask,
modified to provide a second opening in the bottom was used for
the screening studies. This reactor flask was placed on a
rotary evaporator, and, if desired, the contents could be
sprayed uniformly through the second opening while the flask was
rotating. When the second opening was sealed by a glass plate
and an 0-ring seal, the system could be vented through a glass
stopcock mounted on the glass plate. A gaseous reactant could
flush the entire apparatus when the stopcock was in the open
position. After closing the stopcock, the reactor flask and its
contents were rotated and heated (to approximately 185°F) for
10 minutes with a heat lamp. The reactor was then evacuated
using a water aspirator while the heating (to approximately
250°F) and rotation was continued for an additional 10 minutes.
In some instances embrittlement had been so effective that the
rotation of the reactor flask had reduced some of the sample
from 4 inch lengths to fragments 0.4 to 1.2 inches in length.
All samples were subjected to 1 hour of ball milling. (Observa-
tions of this process would indicate that shorter ball milling
times would be adequate) .
The results of these screening studies, summarized in
Table 12 revealed that formaldehyde (as a formalin spray or as
solid polymeric material) could serve as an effective aid in
the embrittlement of paper. Hydrogen chloride (HC1), a strongly
acidic gas, embrittled newsprint even in the absence of formal-
dehyde (entry 12, 13). Weakly acidic reagents such as carbon
dioxide (entry 2), formic acid (entry 4), and acetic acid
(entry 5) failed to produce significant embrittlement even in
the presence of formaldehyde. The nominal embrittlement of
newsprint by sulfur dioxide (entry 6), however, was greatly en-
hanced by the inclusion of formaldehyde in the reaction mixture
(entry 7, 8). The final product obtained after ball milling was
a finely divided brown powder comparable in texture to the
powder obtained from paper embrittled by HC1. Similar products
45
-------
Vacuum Connection
Figure 6. Experimental Arrangement Used for Embrittlement Studies.
-------
resulted from the treatment of newsprint with either chlorine
gas (C12) or thionyl chloride (SOC12) spray.
TABLE 12. CHEMICAL EMBRITTLEMENT OF PAPER SCREENING STUDY
Entry
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
* N.P.
** 1 wt
Paper
Type*
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
N.P.
C.P-
C.P-
C.P.
Treatment Time
(min. )
Formalin 20
Formalin + C02 30
Formalin + N02 45
Formalin + Formic 20
Acid
Formalin + Acetic 45
Acid
S02 20
Formalin + S02 20
Paraformaldehyde 30
+ S02
Methylal + S0? 20
Acetal + SO2 20
Formalin + HC1 20
(gas)
HC1 (gas) 20
HC1 (gas) + H2O 25
SOC12 20
C12 20
C12 + H20 20
Paraformaldehyde 20
+ S02**
Paraformaldehyde 20
+ S02***
Paraformaldehyde 20
+ S02 + H20****
Formalin + S02 20
Formalin + excess 25
S02
C12 20
= Newsprint, C.P. = computer paper
. parafon
naldehyde/10 wt. paper
Results
powder /fragments
powder/ fragments
fragments
no effect
powder/ fragments
fragments
powder
powder
no effect
fragments
powder
powder
powder
powder
powder
powder/fragments
powder/fragments
powder/fragments
powder/fragments
powder /fragments
powder
powder
(bond)
*** 0.3 wt. paraformaldehyde/10 wt. paper
**** 0.15 wt. paraformaldehyde/10 wt. paper/3.5 wt. water
The results of combustion analysis of three of the pow-
ders (Table 13) revealed that some of the reagent was retained
in each of these powders. Care should be taken not to olace
undue significance on these analytical data in comparing the
reagents for retention in the final product. These screen-
47
-------
ing studies did not allow mass balances to be conducted, nor
was an attempt made to measure the concentration of the gaseous
reagents at the outset of the treatments. An effort was made
to maintain experimental conditions to a degree consistent with
efficient screening. Assuming a degree of polymerization (DP)
of 1000 for the cellulose, the data suggest the retention of 61
sulfur atoms per cellulose chain, or approximately one sulfur
per 16 anhydroglucose units. Likewise the 2.18% chlorine anal-
ysis suggests about 1 chlorine per 10 anhydroglucose units,
while the analysis for 5.30% chlorine indicates 1 chlorine for
each 4 anhydroglucose units.
Our understanding of embrittlement mechanisms for the
foregoing reagents is not extensive. A reduction in DP of the
cellulose almost certainly occurs in the presence of acidic
reagents. However, discussions with members of the Forest
Products Laboratory and the Paper Institute assured us that
paper produced from an over-pulped feedstock (lower than normal
DP) would not be expected to be brittle. The extensive incor-
poration of chlorine in the HCl-embrittled naper suggests a
more extensive involvement of HC1 besides acid catalysis of the
hydrolysis process. The replacement of hydroxyl groups in the
cellulose by chlorine, followed by crosslinking via oxygen
bridge formation may be another possible but unproven explana-
tion.
TABLE 13. COMBUSTION ANALYSES OF PAPER POWDERS
(WEIGHT PERCENTAGE)
Reagents
(*)
HC1 + CH20^ ;
ci2
(*)
SO- + CH~0V ;
Carbon
42.80
41.92
36.06
Hydrogen
6.10
5.90
5.84
Chlorine
5.30
2.18
Sulfur
— — — —
1.20
(*) Formaldehyde
Rigidity caused by crosslinking may also be the cause
for embrittlement by formaldehyde and S02. Viscous solutions
containing more than 15% cellulose may be prepared by treating
wood pulp with formaldehyde in a dimethyIsulfoxide (DMSO) solu-
tion. The reaction of cellulose with formaldehyde is generally
thought to result in the formation of methylol cellulose:
Methylol Cellulose
48
-------
Methylol cellulose is expected to be capable of undergoing
crosslinking and reacting with other alcohols and amines. Its
failure to do so in DMSO solution led to the proposed existence
of an ill-defined, cellulose-formaldehyde-DMSO complex.H
The embrittlement observed in our studies might be the result of
the anticipated crosslinking of the methylol cellulose. The
role of S02 and the possible significance of the dipolar, apro-
tic properties of both SO2 and DMSO would deserve further atten-
tion in a more careful, fundamental study.
Embrittlement by thionyl chloride (SOC12) was verified
after HC1 and SO2~induced embrittlement was observed. The
facile hydrolysis of SOC12 by ambient moisture would of course
produce HC1 and SC>2. In addition, however, the direct reaction
of SOC12 with cellulose to yield chlorosulfite esters was also
anticipated. Crosslinking reactions involving these chlorosul-
fite esters might contribute to the embrittlement process. The
expense of the reagent and the experimental difficulty of ob-
taining anhydrous cellulose (to minimize HC1 formation) dis-
couraged us from pursuing this process beyond the stage of
simple observation.
The embrittlement produced by chlorine gas may be
fundamentally different in cause than that of the three fore-
going reagents. Oxidative decomposition of the lignin matrix
in groundwood paper (newsprint) may be at least partially
responsible for the observed effect of chlorine. The reaction
of chlorine with the cellulose itself may give rise to hypo-
chlorites:
Cell - OH + C12 I Cell - O - Cl + HC1
Simple alkyl hypochlorites are thermally unstable and decompose
to a variety of products. In the case of cellulose, these de-
composition reactions may possibly lead to a decrease in DP and
to an increase in the number of carbonyl groups. Crosslinking
reactions between these carbonyl groups and adjacent cellulose
chains may contribute to rigidity and embrittlement.
The possible applications for a refuse-derived powder
might include uses such as a fuel for suspension-fired boilers,
a feedstock for cellulose hydrolysis or hydrogenation reactions,
and as a low density filler in building materials such as wall-
board which do not require load-bearing properties. The unique
properties of such a powder include a high surface area to mass
ratio, which is an obvious advantage in heterogeneous reactions
such as combustion, hydrolysis, and hydrogenation.
6.2 Thermal Treatment
Thermal processing can be employed to obtain solid
fuels. As described earlier, pyrolysis processes have been
49
-------
used for generating carbon char as well as liquid and gaseous
fuels. Similarly, heating in air at moderate temperatures
(212-390°F) can cause cellulose degradation. It has been found
that in some respects heat can have a more degrading influence
on cellulose than a mild acid or oxidizing agent. Free water
adsorbed by the cellulose effectively functions as a plastici-
zer. The major effect of the heat treatment is dehydration,
however, some oxidation and depolymerization also occurs. The
dehydration process causes increased intermolecular hydrogen
bonding and the formation of chemical linkages between adjacent
cellulose molecules. These effects promote cellulose embrittle-
ment, which facilitates the production of powdered fuel from
solid waste. Dehydration and cellulose embrittlement is ob-
served at 300°F. Prolonged heating above 390°F results in the
complete loss in fiber integrity. It would appear that hot
ball milling of the shredded light fraction of MSW in a Har-r
dinge-type mill (air swept conical ball mill) might well be an
effective means for obtaining a powdered fuel.
During this phase of the program a series of experi-
ments were performed to study the effects of thermal treat-
ments alone, and in combination with ball milling. Samples of
shredded newsprint and bond paper, both dry and in a moistened
condition, were exposed to temperatures of 212°F, 300°F, and
390°F for periods of 15 minutes and 30 minutes. For this
series of thermal exposures the samples were placed in a
ceramic crucible and heated in a Leco glo-bar furnace. In
addition, a furnace was designed and constructed to encompass
a set of rollers and a ceramic ball mill jar to permit hot ball
milling of shredded paper samples at temperatures of 212°F,
300°F, and 390°F.
At 212°F no apparent change was observed in any of
the paper samples. At 300°F, oxidation of the paper samples
had begun for the 15 minute exposures and was more pronounced
for 30 minute exposures. At 390°F oxidation was rather exten-
sive for the 15 minute exposures and almost complete through-
out the samples for the 30 minute exposures. The rate of
sample oxidation was more rapid with the newsprint sample. The
moisture content of the samples did not seem to be a factor in
the oxidation rate. The degree of oxidation was judged by the
change in sample color and the degree of sample embrittlement.
It was also observed that the longer the samples were exposed
to temperatures above 300°F the greater the degree of degrada-
tion.
Ball milling the shredded paper samples at 340-385°F
for two to three hours resulted in the conversion to a fine pow-
der. Grinding times of less than one hour were not very effec-
tive. Because of the apparent need for extended grinding times
it may not be feasible to process shredded refuse by hot ball
50
-------
milling alone. A more practical approach may be to combine
chemical embrittlement and hot ball milling.
6.3 Engineering Analysis of a Plant to Produce Powdered
Fuel
A limited engineering analysis was conducted for a plant
to produce a powdered fuel from refuse. The first phase of this
study was the development of a design for a plan to process
1,000 tons of refuse per day. The proposed facility would con-
tain two processing lines (each 30 ton/hr capacity) and would
operate 20 hours per day, six days per week. In the flow plan
developed,the incoming refuse would be screened in a trommel
to separate the minus 4" fraction and open the trash bags. The
oversized (+4") would be shredded and both fractions passed
under magnetic separators to recover the ferrous metal. The
nonferrous fraction would be screened in a trommel to separate
out the fine fraction (minus 1/2") prior to air classification.
The heavy fraction from the air classifier and the fines from
the 1/2" Trommel are burned in an incinerator and provide the
thermal energy required for embrittlement. If aluminum and glass
recovery are desired, this would be accomplished by further
processing the heavy fraction collected from the air classifier.
Aluminum can also be recovered from the incinerated residue but
it would not be of as high a quality. The light fraction ob-
tained from air classification would be embrittled and powdered
in an air swept ball mill (Hardinge Mill). The embrittlement
is accomplished by treating the light fraction with a heated
reagent like HC1 or Cl2/ etc., in the Hardinge Mill. The
powdered material would be swept from the mill entrained in the
reactant gas when it is of the appropriate size. The data used
for developing the flow plan for the propose^ facility were
obtained from University of Dayton studies1^, Combustion
Equipment Associates data reported in U.S. Patent 3,961,91313,
and NCRR studies for New Orleans1 . The flow plan established
for a facility to produce fine powdered fuel from refuse is
presented in Figure 7. The calculations developed for the
material balance used in the flow plan are presented in
Table 14. The flow plan and material balance developed in this
phase of the program served as the basis for determining equip-
ment specifications and operating requirements. This informa-
tion in turn was used to develop the environmental consider-
ations and the economic analysis for the proposed plant in a
subsequent phase of the program.
6.3.1 Environmental Considerations
Recovery of powdered fuel and ferrous metal
results in a reduction of solid waste for disposal and the asso-
ciated environmental problems. However, processing, use and
disposal of the products from this proposed facility could re-
51
-------
RAW REFUSE
in
to
BULKY WASTES
WHITE GOODS,''
TIRES, LOGS,
FURNITURE, ETC
TREE STUMPS'
Figure 7. Resource Recovery Plant to Produce Powdered Fuel.
-------
TABLE 14. MATERIAL BALANCE FOR A POWDERED FUEL PROCESS
U>
Trommel Magnetic Trommel Air
4" Separation 1/2" Classification
o
t*
0
0
iH
»
o
C.
M
Kef use
Organic
Fraction 750
Heta] 1QO
Ferrous 85
Non ferrous 15
Glass and
other inortis 150
i
4J
VI
HI
s
V
rH -~
J-t m
of in
ff
4) r>
3! —
90
9.5
1
n.5
130
J*
0
•H
Jj
tf
n ^>
0) in
c •
-H r-
o cn
C 01
M "-
135
11.5
1
10.5
141
r-l
•H —
•H i/
c tc
in
11.5
1
10.. S
141
r-4
11
•a S
01 P
n f-
111
TJ I/I
3 IT
O ""
"J
2
-
2
~
-------
suit in environmental pollution problems. Waste to energy con-
version facilities and the products generated can contribute to
land, water, and air pollution.15 The potential pollution
problems and associated control technologies for this proposed
embrittlement process have been considered and the areas of
major concern are discussed in the following section.
6.3.1.1 Air Quality
Several potential pollution problems
which have been identified for the proposed process include
dust, and gas emissions from incineration.
Dust emissions are a problem that
plagues most phases of solid waste processing. Shredding, air
classification and screening are major sources of dust emission.
Bacteria and virus emissions are closely associated with dust
since both generally reside on the surface of dust particles.
Effective dust control for the processing requirements of the
proposed facility does not appear to be a problem. Care must be
taken to enclose all processing equipment and conveyors. In
addition, effective exhaust systems must be utilized at the
processing equipment and for the plant in general. Fabric fil-
tration units (baghouses) can be readily employed for cleaning
the exhaust gases, since the gas is at ambient temperature and
the dust is not very abrasive. Pilot studies demonstrated that
99.9% particulate remoyal efficiencies can be obtained with the
use of fabric filters.i5
The other cause of air pollution is the
exhaust gases from incineration of the heavy and fine fractions
which provide the heat source for embrittlement. The uncon-
trolled emissions from this process should be similar to those
reported for most incinerator, operations: particulates, HC1,
SC>2, NOX, CO, and unburned hydrocarbons. CO, NOX, S02 and un-
burned hydrocarbons do not appear to be a problem nor are any
special controls anticipated for these pollutants. HC1 removal
can be achieved with a scrubber unit, however appropriate
materials selection in the design are necessary to inhibit acid
corrosion. Particulate control would probably require an electro-
static precipitator. In addition, since up to 30% of the partic-
ulates could be less than 1 ym, the use of a "fabric filter system
may also be required. Disposal of the fly ash collected is also
of concern due to the presence of trace elements (Cl, Pb, Cu,
Zn, etc.) found in the fly ash.
6.3.1.2 Water Quality
The proposed facility for producing a
powdered fuel relies primarily on dry processing. The only
54
-------
water required is for quenching the incinerator residue and
washing down processing equipment. These waters pick up a con-
siderable amount of contaminants and organics, trace metals,
acids, etc., and will require treatment at a waste water
facility.
6.3.1.3 Solid Wastes
The residue from the proposed facility
will come from the incineration process and is relatively inert.
The captured fly ash and quenched bottom ash will contain a
very small amount of unburned organics (2.5%) and some trace
elements (Be, Hg, Cl, Pb, etc.) requiring proper sanitary land-
fill procedures for its disposal.
6.3.1.4 Environmental Impact of the Powdered
Fuel
The powdered fuel obtained by the
embrittlement process can cause environmental problems in its
use. Combustion of this powdered fuel will produce air
pollutants (particulates, trace metals and gaseous emissions)
similar to those described for the incineration of the heavies
and fine fraction. Of particular concern are the fine parti-
culates, trace metals and the acid vapors. Similar precautions
as those described for incineration will have to be taken to
control these pollutants.
A problem with the powdered fuel which
should also be addressed although it is not usually covered
under environmental concerns is the explosive potential of the
powdered fuel. Fine powders can readily detonate and great
care must be exercised in handling and storage of the powdered
fuel. Several explosions were experienced by A.D. Little and
CEA in their work with powdered fuels. It was reported that the
explosive power of the powdered cellulose was equivalent to half
that attributed to powdered grain. The standard safety prac-
tices established for grain should be followed in the handling
of powdered fuels. In addition to the hazards of explosion by
the dust, there may be a hazard if significant amounts of metal
are in the waste being treated and the embrittlement reagent is
an acid. The hydrogen released by this type of reaction could
present an additional danger and should be avoided. One means
of avoiding this problem would be the use of C12 or some other
nonacid as the embrittlement reagent.
Another approach to handling the
powdered fuel would be to suspend the treated light fraction in
a light fuel oil. Grinding and storage of the treated organics
in a light fuel oil will inhibit explosions and facilitate in-
55
-------
troduction of the powder into the combustion system of a furnace
or boiler.
6.3.2 Economic Considerations
A preliminary economic analysis was prepared for
the powdered fuel process. The analysis is based on the process
flow plan developed (Figure 7). The proposed facility would
operate 20 hours per day. 6 days per week for 52 weeks per year
(265,200 TPY). It is assumed that an adjacent land fill is
available to serve as a backup to the facility. Revenues are
anticipated from:
a) tipping fee
b) sale of recovered metals
c) sale of powdered fuel
The format followed in preparing this economic
analysis was taken from EPA document SW-157.6.10 A summary of
the calculations developed for the capital and operating costs
are presented in Tables 15 and 16 respectively. A summary of
potential revenues are presented in Table 17.
From the analysis developed a total operating
cost per throughput ton of MSW was calculated to be $21.11. A
potential revenue of $10.44/throughput ton was calculated for
the sale of ferrous and the tipping fee. To break even the
powdered fuel would have to sell for about $0.01/lb or about
$1.33/million Btu.
6.4 Conclusions
The use of powdered fuel prepared from the embrittle-
ment of cellulose waste offers a number of advantages:
a) It is more compatible with powdered coal fired
boilers and will have better combustion character-
istics than conventional RDF.
b) It is more readily densified into pellets and will
produce less wear on the extrusion dies.
c) It can be slurried with oil for firing in oil fired
units.
d) It can be used as the feed stock for further chemi-
cal or thermal treatments like hydrolysis, hydro-
genation, gasification, etc.
In the work to date we have identified a number of
chemical treatments for cellulose embrittlement and evaluated
56
-------
TABLE 15. ESTIMATED CAPITAL COSTS (1977 Dollars)
Land (30 Acres @ $10,000/acre) $ 300,000
Site Preparation (35% of land cost) 105,000
Equipment, Installation & Facility Construction 15,456,000
Engineering & Design (6% of 15,681,000) 952,000
Contingencies (10% of 16,813,000) 1,681,000
SUB TOTAL 18,494,000
Legal & Financial Costs (2%) 370,000
TOTAL PLANT COSTS $ 18,864,000
Municipal Revenue Bonds for the Project
(1.12 plant cost) $ 21,128,000
Annual Interest Rate for 20 years @8% 1,095,534
Total Interest to be paid 21,910,669
Total Capital Cost 43,038,669
Annual Capital Cost 2,151,934
Capital Cost Per Ton 8.12
TABLE 16. ESTIMATED ANNUAL OPERATING
AND MAINTENANCE COSTS (1977 Dollars)
Salaries and Benefits $ 872,000
Fuel 100,000
Electricity 437,000
Water and Sewer 3,000
Maintenance 666,000
Residue Removal 250,000
Materials and Supplies 711,000
Taxes (.75%) 142,000
Insurance and Management Costs ($l/ton) 265,000
Total Annual Operating & Maintenance Cost 3,446,000
Operating and Maintenance Cost Per Ton 12.99
57
-------
TABLE 17. POTENTIAL REVENUE SOURCES
Revenue Source Dollars/Throughput Ton
Tipping Fee 8.50
Ferrous Metal (86 TPD @ a net cost of $22.55/ton) 1.94
Powdered Fuel (550 TPD) ??
Cost/ton 21.11
Cost needed for sale of fuel to break even 10.67
$.01/lb of powdered fuel @ 7,500 Btu/lb - 1.33/M Btu
their effectiveness in laboratory studies. In addition a pre-
liminary design for a resource recovery plan to produce powdered
fuel was developed. This design plan was the basis for a pre-
liminary economic analysis. From the data developed it was
calculated that the powdered fuel would have to sell for about
$0.01/lb for a facility having a tipping fee of $8.50.
58
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SECTION 7
LIQUID AND GASEOUS FUELS FROM THE ORGANIC
FRACTION OF MUNICIPAL SOLID WASTE
A number of processes have been developed for obtaining
liquid and gaseous fuels from refuse. The literature contains
descriptions of a wide range of liquefaction and pyrolysis pro-
cesses in full scale operation, in demonstration, in pilot plant
development, and in the laboratory. The major processes have
been identified and are described in the background section of
this report. During this project two laboratory processes were
also reviewed:
a) the Worcester Polytechnic Institute (WPI) hydrogena-
tion-liquefaction process; and
b) the Wright-Malta Corporation (WMC) steam injection
pyrolysis process.
Although both of these processes offer an interesting
potential, their scale-up at the present time poses a number of
difficulties. In the WPI process the organic fraction of solid
waste is converted to a fuel oil. In this hydrogenation reac-
tion one ton of solid waste generates 2.15 barrels of oil. The
Wright-Malta Corporation has developed an interesting steam
pyrolysis process for garbage and sewage sludge in a rotary
kiln. In the WMC process, gaseous and liquid fuels are obtained.
7.1 The Worcester Polytechnic Institute Process
Kaufman and Weiss of Worcester Polytechnic Institute
(WPI) conducted pilot olant studies on the hydrogenation-lique-
faction of cellulose.17 A 20 wt percent slurry of shredded
paper (cellulosic material) in mineral oil was subjected to 1029
psia H2 at 845°F for 15.1 min in the presence of 0.04 wt percent
Ni(OH)2 catalyst. Under these conditions 1 Ib of newsprint in
4.4 Ibs of oil produced 4.9 Ib of product oil, 0.1 Ib CO, 0.07 Ib
CO2, 0.001 Ib CH4, 0.07 Ib C2 - £4 hydrocarbons and 0.2 Ib of
solid residue. The product oil, projected to be 2.15 bbl/ton of
refuse, had a heating value of 17682.2 - 18527.6 Btu/lb and an
oxygen content below 1 percent. Analysis of the solid residue
indicated its composition to be 58.5 percent C, 4.75 percent Hf
19.8 percent 0, and 16.95 percent others (by difference).
59
-------
The conversion of cellulose to volatile products is
thought to proceed via consecutive reactions.2^ (Cellulose^—•*>
pyrobitumens ^••••^-oil^^—a^-gas). Formation of pyrobitumens as
a first step in the conversion is well known, and involves ther-
mal dehydration, depolymerization, and removal of CO. The WPI
process is therefore in reality the catalytic hydroliquefaction
and/or hydrogasification of pyrobitumens, which are defined as
benzene-insoluble materials containing C, H, and 0 in varying
proportions.
The reaction of organic compounds with hydrogen may in-
volve the addition of hydrogen across a double bond (called
hydrogenation) as in the conversion of ethylene to ethane, or it
may require the replacement of an atom or group of atoms by
hydrogen (called hydrogenolysis). Both processes are very slow
in the absence of catalysts at room temperature and low pressure.
Inclusion of catalysts such as Ni, Pd, Pt, Rh, or Ru frequently
permits the desired reaction to proceed easily and rapidly under
the foregoing conditions. Reaction is thought to occur on the
metal surface. Since all hydrogenation reactions of carbon-
double bonds are exothermic (4.5 x 104 - 5.4 x 10^ Btu/lb mole),
activation energies (Eac-t-) may become quite low with suitable
catalysts. Gupta, Kranich, and Weiss calculate Eact for the
catalytic hydrogenation of ot-cellulose to be 3.09 x 104 Btu/lb
mole.
The conversion of cellulose to a hydrocarbon requires
that hydrogen replace the oxygen atoms in cellulose. Such re-
placement may occur by direct substitution (i.e. hydrogenolysis),
or by initial dehydration followed by addition of hydrogen
across the double bond (i.e. hydrogenation).
Kaufman and Weiss reported DTA (differential thermal
analysis) results showing hydrogenation exotherms between 390°F
and 480°F. This temperature range is curiously close to the
temperature range of initial water evolution during cellulose
pyrolysis experiments. Infrared spectral data19 suggest the
formation of anhydrocellulose at 410°F during pyrolysis. In
addition, hydrogenolysis reactions are not common with saturated
compounds (no double bonds) such as cellulose. (See Figure 8).
According to Kaufman and Weiss (p. 138), a crude
approximation of the stoichiometry for the WPI process is:
4 C6H1Q05 + 12 H2 i I C6H14 + C12H26 + 4 CO + 2 C02 + 12 H2.
Their flow plan is presented in Figure 9 -
60
-------
CH2OH
CH2OH
Anhydrocellulose
etc
Figure 8. Cellulose Hydrogenation
The WPI investigators proposed a 36 ton/day plant for
Holden, Massachusetts designed to process a 50 wt percent ref-
use-oil slurry. Inorganics and organics were to be source-
separated. The organics were to be treated in a hammermill
prior to being slurried with oil. The upper limit to particle
size was never determined, but the investigators were interested
in investigating chemical embrittlement to produce a powdered
feedstock. Due to lack of funding, the Holden, Massachusetts,
facility was never built. Cost of oil production in a proposed
36 ton/day pilot plant was projected to be $24.77/bbl. It was
estimated that plants processing 500-2,000 tons daily could pro-
duce oil for $4.00 to $5.92 per barrel. This projection would
appear to be extremely optimistic, based on available informa-
tion.
The chief advantage of the WPI method is the production
of a high quality heating oil which should be readily market-
able. Among the disadvantages one must considerable are:
a) high capital costs for a high pressure, hydrogenation
system, and the associated maintenance problems, anti-
cipated scale-up problems,
61
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-SHREDDED MSW
INORGANICS
INORGANIC*
REMOVAL
ORGAN ICS (55%)
INORGANICS (25%)
MOISTURE (20*1
ORGAN ICS
INORGANICS } @70°F 6" size
MOISTURE
niri-Timr J MOISTURE
MOISTURE REDUCTION
i
ORGANICS
INORGANICS
MOISTURE
FINE GRINDING
TATAI YCT
HEAVY OIL ' '
• iLU
ORGANICS
INORGANICS
MOISTURE
RRY
PREPARATION
TANK
_,
o
3
Lkl
°Z u
1 ,
ORGANICS
HEAVY OIL
INORGANICS
MOISTURE
CATALYST
REACTOR
GAS 800°F
1
T
H2
CO
CH4
c2-c4
• 8212°F
)
} @70°F
1
' @173°F
RESIDUES
C02 *
OIL
1
CATALYST
CHAR
INORGANICS
H20
•INORGANIC REMOVAL MAGNETIC SEPARATION. TROMMEL SCREEN & AIR CLASSIFIER
Figure 9. Flow Plan for the WPI Process.
62
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b) inherent danger involved in a large scale use of hy-
drogen under pressure,
c) the need to reduce the refuse to fine particles for
the reaction, and
d) the disposal of the residue (20 weight percent of the
starting material) and the liquid effluents.
The source of the CO and C02 in the WPI process is pro-
posed to be the water gas shift reaction which produces as a
third product sufficient H2 to supply about 50% of that required
for hydrogenation. An examination of the product composition
(tables, p. 129; chromatograms, p. 112, and 133) 17 indicates
that the suggested stoichiometry is indeed a very crude approxi-
mation. Besides neglecting numerous minor products, the equa-
tion postulates the formation of saturated non-cyclic hydrocar-
bons as the major products. Hexane would have the composition
83.63% C, 16.3% H, and the hydrogen: carbon ratio would be
2.33:1. Dodecane would be 84.61% C, 15.39% H, and would have a
hydrogen: carbon ratio of 2.17:1. The WPI product oils have
H:C ratios which are too low to be non-cyclic, saturated hydro-
carbons (1.82-1.97, p. 131). The carbon contents are 2-3% too
high, and the hydrogen contents are too low by similar amounts.
The H:C ratios for the WPI oils indicate that they might better
be represented by formulas such as C^H^g or C^QH2o (i.e., 2-4
hydrogen atoms less than required for saturation). These dis-
tinctions are only important if one requires a balanced equation
for subsequent thermochemical calculations. Such calculations
are fraught with difficulties owing to the complexities of the
reactions (many products, some of undetermined composition). A
flow plan, material balance, and economic evaluation were pre-
pared by Kaufman and Weiss for their process.
7.2 The Wright-Malta Corporation Process
Injection of steam during the pyrolysis of municipal
solid waste was undertaken by the Wright-Malta Corporation.20
Their studies have been limited to small scale laboratory ex-
periments with an electrically heated desk-top rotary kiln,
temperatures to 1112°F and 441 psia steam. Evolution of CO and
C02 begins at 300°F, followed by condensable liquids. Methane
evolution begins at 570°F. The gas mixture will burn when the
pyrolysis temperature rises to 750°F, and by 1112°F the gas is
nearly pure C02 and H2 in a 1:2 ratio as required by the stoi-
chiometry of the water-gas reaction.
C + 2 H20 —^C02 + 2 H2
The WMC workers found that the inclusion of 10 wt percent Na2C03
(soda ash) resulted in a decrease in the amount of char residue,
and in a tendendy for the liquid pyrolysate to be less soluble
in water. At 14.7 psia steam, for example, the char residue
63
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decreased from 23 wt percent to 15 wt percent in the presence of
soda ash. A six percent char residue was obtained with 441 psia
steam, 930"F, and a heating time of 1.5 hr. In the projected
plant, coarsely shredded refuse would be introduced through a
double lock hopper into the high end of an inclined rotary kiln.
Heat would be supplied by a counterflow of superheated steam,
the temperatures ranging from 100°F at the high end to 1112°F
at the low end. The tumbling action of the kiln, enhanced by
cans, bottles, rocks, or intentionally added "breakers", would
reduce the refuse to gas and a solid residue.
The expected fuel gas emerging from a projected plant
would be 70% 1^0 vapor, 14% steam, and 15% combustible gases.
Its heating value would be about 140 BTU/scf. The residue is
expected to represent 30-40% of the original mass and 10% of the
original volume. It could be processed to reclaim glass and
metals.
Pilot studies actually conducted in the desk-top kiln did
not use counter-current steam heating, nor was the process
continuous. A batch process was employed, and the temperature
was raised uniformly by electrical heating. As a result, liquid
pyrolysate was obtained (57-84% of the original mass by differ-
ence) in addition to gases (10-20%) and a char residue (5-23% of
the original mass). The liquid was not analyzed.
The benefits as stated by WMC include:
1. no fine shredding, drying, or classifying is
necessary;
2. sewage sludges may be employed as part of the feed-
stocks;
3. a theoretical system efficiency of 40-45% is achieved,
which claimed to be comparable to that of the best
combined cycle systems operating on natural gas or
liquid fuels.
In reviewing the Wright-Malta process, the following
potential problem areas have been identified:
1. maintenance on the necessary rotating seals and inter-
locks;
2. corrosion induced by decomposition of chlorinated
polymers (e.g. PVC)
3. the availability of a market for the product fuel gas.
(Perhaps the liquid pyrolysate would be more desir-
able .)
64
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7.3 Conclusions
In this phase of the project two laboratory processes for
liquefaction/gasification described in the literature were re-
viewed. Although both processes were considerably different than
the conventional pyrolysis processes, they appeared to offer
some interesting potential for enhanced fuel recovery. In study-
ing these processes the major problems for commercial scale-up
were identified. In addition to the technical problems anti-
cipated it is believed that the economics of either process
would not be viable at this time.
65
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Presented by the Resource Recovery Division, Office of
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66
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11. Hammer, R.B. et al. Process and Fiber Spinning Studies for
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67
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APPENDIX I
BIBLIOGRAPHY
CONCEPTS FOR IMPROVING FUEL FRACTION OF SOLID WASTE
Compiled by:
Norman L. Hecht
Donovan S. Duvall
University of Dayton
Research Institute
300 College Park Drive
Dayton, Ohio 45469
68
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TABLE OF CONTENTS
Page
COMBUSTION THEORY FOR SOLID WASTES 71
PYROLYSIS OF SOLID WASTES 71
PYROLYSIS PATENTS 75
THERMAL DECOMPOSITION OF CELLULOSE 75
CARBONIZATION PATENTS 80
HYDROLYSIS 81
RENEWABLE FUELS 82
LIQUEFACTION 83
BIO-CONVERSION 84
OZONE TECHNOLOGY 85
ALLIED INDUSTRIAL PROCESSES 86
PAPER RECYCLING 87
FIBER RECOVERY 87
INDUSTRIAL WASTES 89
SHREDDERS 91
GRAVITY SEPARATION 9 2
UNIT OPERATIONS 92
WASTE MANAGEMENT REPORTS TO CONGRESS 93
ECONOMICS OF WASTE MANAGEMENT 94
GENERAL RESOURCE RECOVERY ARTICLES 95
AKRON 10 2
AMAX 102
AMES, IOWA 102
BUREAU OF MINES 103
COLUMBUS, OHIO 103
COMBUSTION EQUIPMENT ASSOCIATES - ECO FUEL 103
CONNECTICUT 104
C.P.U 104
FOSTER WHEELER COPROATION - LIVINGSTON, N.J 104
FRANKLIN 104
FT. WAYNE & G.M. - CUBETTES 105
NCRR
69
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TABLE OP CONTENTS (Concluded)
NEW YORK 105
ST. LOUIS - UNION ELECTRIC 105
TULSA, OKLAHOMA 107
OTHER RESOURCE RECOVERY PROJECTS 107
CONFERENCES 108
70
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COMBUSTION THEORY FOR SOLID WASTES
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PYROLYSIS OF SOLID WASTES
Anon., "Pyrolysis of Refuse Gains," Environmental Science and
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Bailie, Richard C., and Alpert, Seymour, "Conversion of Muni-
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Bailie, Richard C., and Ishida, Masaru, "Gasification of Solid
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Baum, Bernard, and Parker, Charles H., Solid Waste Disposal,
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Cruz, Ibarra E., "Studies on the Production and Utilization of
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I
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Components," Combustion, May 1968.
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1956.
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CARBONIZATION PATENTS
Abbott, W.F., "Method for Carbonizing Fibers," U.S. Patent No.
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HYDROLYSIS
Ahmad, Ch. Manzoor, and Malik, M.N., "Studies on Saccharification
of Conifer Wood-Waste: I. Effect of Varied Concentration of
H2S04 and Period of Heating on Initial Hydrolysis and
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Anon., "Will Old Newspapers Make a Good Chemical Brew?" Chemical
Week, 115(5):33, July 31, 1974.
Andren, Robert K. and Nystrom, John M., Pilot Scale Production
of Cellulose and Enzymatic Hydrolysis of Waste Cellulose,
Food Sciences Laboratory, U.S. Army Natick Development Center,
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Andren, Robert K., Mandels, Mary H. and Medeiros, John E.,
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Hydrolysis. I. Primary Evaluation of Substrates," Applied
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Andren, Robert K., Mandels, Mary H. and Medeiros, John E.,
Production of Sugars from Waste Cellulose by Enzymatic
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Andren, Robert K., and Erickson, Richard J., The Enzymatic
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Chang, M., Pound, T.C., and Manley, R. St. John, "Gel-Permea-
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Chapman, Richard A., Acid Hydrolysis of Cellulose in Municipal
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Converse, A.O. et al., Acid Hydrolysis of Cellulose in Refuse
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Pagan, Robert D., Acid Hydrolysis of Refuse, U.S. Environmental
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Harris, John P., "Acid Hydrolysis and Dehydration Reactions for
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Holtiezer, H.W. and Tilloson, A.H., "Hydrolysis Process for
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Kunz, Nancy D., Gainer, John L., and Kelly, James L., "Effects
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1972.
Nystrom, John M., Equipment and Instrumentation Requirements
for Cellulose/Cellulose Processing, U.S. Army Natick Develop-
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Nystrom, John M., Andren, Robert K., and Allen, Alfred L.,
Enzymatic Hydrolysis of Cellulosic Waste: The Status of
the Process Technology and an Economic Assessment, U.S. Army
Natick Research and Development Command, 12 April 1976.
Porteous, Andrew, "Cellulose Material Into Alcohol," Paper
Trade Journal, February 7, 1972.
Porteous, Andrew, "The Recovery of Industrial Ethanol from
Paper in Waste," Chemistry and Industry, 6 December 1969.
Shinouda, H.G., and Fleita, D.H., "Infrar-red Study on the
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Visapaa, Asko, "Heterogeneous Acid Hydrolysis of Cellulose,
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Technical Research Centre of Finland, Laboratory of Chemistry,
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RENEWABLE FUELS
Anon., "Outlook Bright for Methyl-Fuel," Environmental Science
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82
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Bachman, W.A., "U.S. Winter-fuels Supply Situation Looks
Precarious," The Oil and Gas Journal, October 1, 1973.
Davis, John C., "Can Methanol Fuel Contend?" Chemical Engineering,
June 25, 1973.
Dutkiewicz, Bronek, "Methanol Competitive with LNG on Long
Haul," The Oil and Gas Journal, April 30, 1973.
Ganeshan, R., "Methanol as Fuel - Cheaper than LNG," The Oil
and Gas Journal, July 24, 1972.
Jones, F.L. and Vorres, K.S., Clean Fuels from Coal - An
Alternative to SNG, The Babcock & Wilcox Company, Alliance
Research Center, Alliance, Ohio, undated.
Mills, G. Alex and Harney, Brian M., "Methanol—The 'New
Fuel1 from Coal," Chemtech, January 1974.
Paulsen, T.H., "Methyl-fuel Project Serves as an Attractive
Petrochemical Base," The Oil and Gas Journal, October 1, 1973.
Royal, M.J. and Nimmo, N.M., "Big Methanol Plants Offer Cheaper
LNG Alternatives," The Oil and Gas Journal, February 5, 1973.
LIQUEFACTION
Anon., "From Agricultural Wastes to Feed or Fuel," Chemical
and Engineering News, Vol. 50, No. 32, May 29, 1972, pp. 14-
15.
Appell, H.R., et al., "Conversion of Urban Refuse to Oil,"
Bureau of Mines Solid Waste Program, U.S. Department of
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Appell, H.R., et al., "Conversion of Cellulosic Wastes to Oil,"
Report of Investigations No. 8013, U.S. Department of the
Interior, Bureau of Mines, 1975.
Cox, John L. et al., "Conversion of Organic Waste to Fuel Gas,"
Journal of the Environmental Engineering Division, EE3,
June 1974.
Demmitt, T.F., Liquefaction of Coal and Cellulosic Wastes at
High Temperature and Pressure, Battelle Pacific Northwest
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Feldman, Herman F., "Pipeline Gas from solid Wastes," AlChe
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83
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Feldman, Herman F., "Process for Converting Solid Wastes to
Pipeline Gas," U.S. Patent No. 3,733,187, May 15, 1973.
Gupta, Dharam V. et al., "Catalytic Hydrogenation and Hydro-
cracking of Oxygenated Compounds to Liquid and Gaseous Fuels,"
I&EC Process Design and Development, Vol. 15, No. 2, pp. 256-
260, April 1976.
Kaufman, J.A. et al., "Catalytic Hydrogenation of Solid Waste
Carbohydrates to Fuel Oil," Chemical Engineering World,
Vol. IX, No. 4, April 1974.
Kaufman, James A. and Weiss, Alvin H., Solid Waste Conversion:
Cellulose Liquefaction, Worcester Polytechnic Institute,
February 1975.
Weiss, Alvin H., "Conversion of Solid Waste to Liquid Fuel,"
Textile Research Journal, September 1972, pp. 526-533.
Wender, Irving et al., "Clean Liquid and Gaseous Fuels from
Organic Solid Wastes," Chapter 2 in Recycling and Disposal of
Solid Wastes, ed. by T.F. Yen, Ann Arbor Science Publ., Ann
Arbor, Mich., 1974, pp. 43-99.
BIO-CONVERSION
Anderson, Larry L., Energy Potential from Organic Wastes: A
Review of the Quantities and Sources, U.S. Department of
the Interior, Bureau of Mines, Information Circular 8549,
1972.
Anon., "IGT Weighs Potential of Fuels from Biomass," C&EN,
February 23, 1976, pp. 24-26.
Bohn, Hinrich L., "A Clean New Gas," Environment, Vol. 13,
No. 10, December 1971.
Callihan, C.D., and Dunlap, C.E., Construction of a Chemical-
Microbiol Pilot Plant for Production of Single-Cell Protein
from Cellulosic Wastes, Louisiana State University, 1971.
Clemons, Clarence A., "Biogas Recovery from Solid Wastes,"
News of Environmental Research in Cincinnati, U.S. Environ-
mental Protection Agency, September 15, 1976.
Cooney, Charles L. et al., Fuel Gas Production from Solid
Waste, Dynatech R/D Company, NSF-RANN-74-112, 31 July 1974.
Dugas, Doris J., Fuel from Organic Matter, Rand Corporation,
Santa Monica, Calif., October 1973.
84
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Hitte, Steven J., Anaerobic Digestion of Solid Waste and Sewage
Sludge to Methane, U.S. Environmental Protection Agency,
Solid Waste Information Report SW-159, July 1975.
Kirk, T. Kent, Lignin-Degrading Enzyme Systems, Forest Products
Laboratory, Forest Service, U.S. Department of Agriculture,
1975.
Kispert, R.G. et al., Fuel Gas Production from Solid Waste,
Dynatech Research and Development Corp., Report No. 1258,
undated.
Leatherwood, J.M., "Utilization of Fibrous Wastes as Sources of
Nutrients," North Carolina State University Department of
Animal Science, 1973.
Maugh, Thomas H. II, "Fuel from Wastes: A Minor Energy
Source," Science, Vol. 178, 10 November 1972.
Pfeffer, John T., Reclamation of Energy from Organic Waste,
Department of Civil Engineering, University of Illinois,
March 1974.
Shuster, William W., Partial Oxidation of Solid Organic
Wastes, Polytechnic Rensselaer Institute, 1970.
Stutzenberger, F.J. et al., "Cellulolytic Activity in Municipal
Solid Waste Composting," Canadian Journal of Microbiology,
Vol. 16, pp. 553-560.
OZONE TECHNOLOGY
"Check Into I.O.I.," International Ozone Institute membership
brochure, undated.
Liebergott, Dr. Norman, Use of Ozone in the Pulp and Paper
Industry for Pulp Bleaching, Pulp and Paper Research Insti-
tute of Canada, Point Claire, Quebec, Canada, undated.
Ozonews, publication of the International Ozone Institute,
Inc., Vol. 1, Nos. 1 (Oct. 1974), 2 (Nov. 1974), 3 (Dec. 1974);
Vol. 2, Nos. 1 (Jan. 1975), 2 (Feb. 1975).
Soteland, N., "Bleaching of Chemical Pulps with Oxygen and
Ozone," The Norwegian Pulp and Paper Research Institute,
Pulp and Paper Magazine of Canada, Vol. 75, No. 4, pp. 153-
158, 1974.
85
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Soteland, N. and Loras, V., "The Effect of Ozone on Mechani-
cal Pulps," The Norwegian Pulp and Paper Research Institute,
Norsk Skogindustri, Vol. 28, No. 6, pp. 165-169, 1974.
ALLIED INDUSTRIAL PROCESSES
Alter, Harvey, and Ingle, George, "Coatings Wastes as Energy
Sources," National Center for Resource Recovery, Inc.,
Washington, D.C., April 1, 1974.
Anon., "Let Residual Disposal Pay for Itself," Power,
February 1971.
Auerbach Associates, Inc., A Study of Flame Retardants for
Textiles, Environmental Protection Agency Report No. EPA-
560/1-76-004, February 1976.
Cashen, Norton A. and Mason, Austin C.F., "Laboratory Apparatus
for Treating Cotton and Cotton-Blend Textiles with Organic
Solvent Vapors," U.S. Patent No. 3,872,693, March 25, 1975.
Claviez, E., "Machine for Making A Compound Paper and Fiber
Material," U.S. Patent No. 983,266, February 7, 1911.
Copeland, G.G., "Industrial Waste Disposal by Luidized Bed
Oxidation," AIChE Symposium Series, Solid Waste Treatment,
Vol. 68, No. 122, pp. 63-72.
Copeland, G.G., and Hanway, John E. Jr., "Treating Waste
NSSC Liquors in a Fluidized-Bed Reactor," Paper Trade
Journal, October 14, 1963.
DeSpain, J.R., "Vibratory Feeding of Bark Burning Boilers,"
Carrier Division, Rex Chainbelt, Inc., Louisville, Kentucky,
undated.
Fanger, G.O. et al., "Microcapsules and Methods of Making Same,"
U.S. Patent No. 3,843,557, October 22, 1974.
Feld, I.L. et al., "Process for Wet Grinding Solids to Extreme
Fineness," U.S. Patent No. 3,075,710, January 29, 1963.
Gillette Company Research Institute, "The Nitrite-Accelerated
Photochemical Degradation of Cellulose as a Pretreatment for
Microbiological Conversion to Protein," EPA-670/2-73-052,
July 1973.
Gorham International, Inc., Study of Solid Waste Management
Practices in the Pulp and Paper Industry, Environmental
Protection Agency Report No. SW-80c, Feburary 1974.
86
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Harkin, John M. and Rowe, John W., Bark and Its Possible Uses,
U.S.D.A. Forest Products Laboratory Research Note No. FPL-
091, revised 1971.
Hatch, L.T., Sharpin, R.E., and Wirtanen, W.T., "Chemical/
Physical and Biological Treatment of Wool Processing Wastes,"
EPA-660/2-73-036, January 1974.
Mathur, Kishan B. and Epstein, Norman, "Developments in Spouted
Bed Technology," The Canadian Journal of Chemical
Engineering, Vol. 52, April 1974.
Oregon State University, "The Chemical Conversion of Solid
Wastes to Useful Products," EPA-670/2-74-027, April 1974.
Suda, S., "Fuels and Their Effects on Power Design for the Pulp
and Paper Industry." American Paper Industry, January 1974.
Wahl, Diana and Bancroft, Raymond L., "Solid Waste Management
Today...Bringing About Municipal Change," Nation's Cities,
August 1975,
Wilson, W.K. and Parks, E.J., An Analysis of the Aging of Paper:
Possible Reactions and Their Effects on Measurable Pro-
perties, National Bureau of Standards, NBSIR-74-499,
April 1974.
PAPER RECYCLING
Dane, Sally, The National Buyer's Guide to Recycled Paper.
Washington, D.C.: Environmental Educators, Inc., 1973.
Lingle, Steven, Separating Paper at the Waste Source for Re-
cycling, U.S. Environmental Protection Agency, Office of
Solid Waste Management Programs Report SW-128, 1974.
Lingle, Steven, Paper Recycling 1973: A Dramatic Year in
Perspective, U.S. Environmental Protection Agency, Office
of Solid Waste Management Programs, 1975.
Miller, Elton Eugene, "The Utilization of Waste Paper That Is
Interleaved with Carbon Paper," Army Material Command,
Texarkana, Texas, July 1971.
News release, October 21, 1976, American Paper Institute
FIBER RECOVERY
Auchter, Richard J., "Future Wood Needs for Papermaking Fibers
87
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Should Not Be a Problem," Paper Trade Journal, August 23,
1971.
Auchter, Richard J., "Recycling Forest Products Retrieval from
Urban Wastes," Forest Products Journal, Vol. 2, No. 2,
pp. 12-15, February 1973.
Carr, Wayne F., Increased Wood Fiber Recycling: A Must, Forest
Product Laboratory, Forest Service, U.S. Department of
Agriculture, 1969.
Carr, Wayne F., "Value Recovery from Wood Fiber Refuse," Pro-
ceedings of the Second Mineral Waste Utilization Symposium,
sponsored by U.S. Bureau of Mines and IIT Research Institute,
March 1970.
Carr, Wayne F., "Many Problems Involved in Increasing Utilization
of Waste Paper," Paper Trade Journal, May 17, 1971.
"Dividends from Wood Research," listings of publications of the
Forest Products Laboratory, Forest Service, U.S. Department
of Agriculture. Listings dated: 1975, July 1975, January
1976, July 1976.
"Forest Products Laboratory List of Publications on the Chemistry
of Wood," U.S. Department of Agriculture, Forest Service,
September 1968.
Forest Products Laboratory Solid Waste Separation Research,
U.S. Department of Agriculture, Forest Service, undated.
Klungness, John H., "Recycled Fiber Properties as Affected
by Contaminants and Removal Processes," U.S. Department of
Agriculture, Forest Service Research Paper No. FPL 223, 1974.
Laundrie, James F., Recovery and Refuse of Wastepaper from
Shredded Household Trash, U.S. Department of Agriculture,
Forest Products Laboratory, Forest Service, undated.
Laundrie, J.F., "Separation of Thermoplastic Film and Waste-
paper," U.S. Patent No. 3,814,240, June 4, 1974.
Laundrie, James F., "Study Indicates Dry Recovery of Paper from
Shredded Trash May Be Feasible," Paper Trade Journal,
January 13, 1975.
Laundrie, J.F. and Klungness, J.H., Effective Dry Methods of
Separating Thermoplastic Films from Wastepaper, U.S. Depart-
ment of Agriculture, Forest Products Laboratory, Forest
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88
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Laundrie, J.F. and Klungness, J.H., "Dry Methods of Separating
Plastic Films from Waste Paper," Paper Trade Journal,
February 5, 1973.
Mohaupt, A.A. and Koning, J.W., "A Practical Method of Re-
cycling Wax-Treated Corrugated," Boxboard Containers,
January 1972.
Mohaupt, A.A. and Koning, J.W. Jr., "Corrugating Medium from
Household Trash," Tappi, Vol. 57, No. 11, November 1974.
Myers, Gary C., Household Separation of Wastepaper: FPL
Employee Survey, U.S. Department of Agriculture, Forest
Products Laboratory, Forest Service, Research Paper No.
FPL 159, 1971.
Myers, Gary C., "What's in the Wastepaper Fiber Collected from
Municipal Trash," Paper Trade Journal, August 30, 1971.
Neville, Charles B. Jr., and McDermott, Bernard A., "How
District Heating/Cooling and Solid Waste Disposal Became
Part of a Downtown Urban Renewal Project," Specifying
Engineer, February 1976.
Pearce, Arthur, "Garbage-In, Fuel-Out," Fairfield County
(Connecticut), May 1975.
Solid Waste Recycling Research, U.S. Department of Agriculture,
Forest Service, March 1972.
INDUSTRIAL WASTES
Albrecht, Oscar W., "Impediments to Recycling Obsolete Ferrous
Scrap," Public Works Magazine, October 1972.
"Aluminum Can Recycling Centers," The Aluminum Association,
New York, N.Y., 1973.
Anon., "Copper Industry Uses Much Scrap Iron," Environmental
Science and Technology, Vol. 7, No. 2, February 1973.
Battelle Memorial Institute Columbus Laboratories, A Study
to Identify Opportunities for Increased Solid Waste Utili-
zation. U.S. Environmental Protection Agency Reports:
Vol. I, EPA-SW-40D.1-72, 1972; Volumes II-VII, EPA-SW-
40D.2-72, 1972; Volumes VIII and IX, EPA-SW-40D.3-72, 1972.
Bourcier, Gilbert F. et al., Recovery of Aluminum from Solid
Waste, Reynolds Metals Company, Richmond, Virginia, 1972.
89
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Games, Richard, Industrial Solid Waste Classification Systems,
Arthur D. Little, Inc., June 1974.
Cheremisinoff, P.E. and Young, Richard A., "Industrial Solid
Waste Handling and Disposal—A Special Staff Report,"
Pollution Engineering, June 1974.
Froisland, L.J. et al., Upgrading Junk Auto Shredder Rejects,
U.S. Department of the Interior, Bureau of Mines, Solid
Waste Research Program Technical Progress Report, 1972.
Gordon, Richard L., The Collection of Nonferrous Scrap: A
Literature Review of the Copper and Aluminum Sectors, U.S.
Department of the Interior, Bureau of Mines, Open-File
Report 19-72, July 1972.
Gordon, Richard L. et al., Effective Systems of Scrap Utili-
zation: Copper, Aluminum, and Nickel, Pennsylvania State
University, July 1972.
Incentives for Recycling and Reuse of Plastics, Arthur D. Little,
Inc., U.S. Environmental Protection Agency Report SW-41c.l,
1973.
Ostrowski, E.J., Evaluation of Eidal Mill Processed Solid Waste
Ferrous Scrap from St. Louis, Missouri, Solid Waste
Recovery System, National Steel Research Corp., 1973.
Regan, W.J. et al., Identification of Opportunities for In-
creased Recycling of Ferrous Solid Waste, U.S. Environ-
mental Protection Agency Report No. EPA-SW-45D-72, 1972.
"Report to Congress on Hazardous Waste Disposal," U.S.
Environmental Protection Agency, June 30, 1973.
Resource Engineering Associates, State of the Art Review on
Product Recovery, U.S. Department of the Interior, Federal
Water Pollution Control Administration, Water Pollution Con-
trol Research Series - 17070 DVW 11/69, November 1969.
Saxton, James C. and Kramer, Marc, Industrial Chemicals Solid
Waste Generation, International Research and Technology
Corporation, IRT-325-R, June 1974.
Sorg, Thomas J., Industrial Solid Waste Problems, AIChE
Symposium Series, Vol. 68, No. 122, 1972.
Theis, James M., Waste Problems in 2,4-D Manufacture Solved
by Use of High Purity Intermediates and Total Recycle, The
Dow Chemical Company, June 1973.
90
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SHREDDERS
Anon., "Another Lesson In Resource Recovery," Environmental
Science and Technology, Vol. 7, No. 10, October 1973.
Anon., "First Lesson in Resource Recovery," Environmental
Science and Technology, Vol. 7, No. 4, April 1973.
Anon., "Special 'News' Processing System Produces High Density
Bales Called 'Super' Grade by Mills," Secondary Raw
Materials, October 1972.
Anon., "Shredded Bulky Rubbish Used as Daily Cover," Solid
Wastes Management Refuse Removal Journal, March 1973.
Pales, Ed, "Now Giant Grinders Gobble Our Waste Problem,"
Popular Science, February 1974, pp. 109-111, 152.
Midwest Research Institute, Kansas City, Size Reduction Equip-
ment for Municipal Solid Waste, U.S. Environmental Pro-
tection Agency Report EPA-530/SW-53c, 1973.
Rogers, Harvey W. and Hitte, Steven J., Solid Waste Shredding
and Shredder Selection, U.S. Environmental Protection
Agency Report No. SW-140, November 1974.
Sales brochure, American Baler Company, Bellevue, Ohio.
Savage, G. and Trezek, G.J., "Screening Shredded Municipal
Solid Waste," Compost Science, January/February 1976.
Savage, George and Trezek, George, Size Reduction in Solid
Waste Processing, Refuse Size Reduction Facility, College of
Engineering, University of California—Berkeley, undated.
Savage, George, Size Reduction in Solid Waste Processing,
Aluminum Can Shredding Experiments, College of Engineering,
University of California—Berkeley, undated.
"Shredders," fact sheet from the National Center for Resource
Recovery, Inc., April 1973.
Trezek, George J. , Size Reduction in Solid Waste Processing:
First Year Progress Report 1971-1972, College of
Engineering, University of California—Berkeley. 1972.
Trezek, George, Obeng, Dennis M., and Savage, George, Size
Reduction in Solid Waste Processing: Second Year Progress
Report 1972-1973, College of Engineering, University of
California—Berkeley, 1974.
91
-------
Trezek, George J. and Savage, George, Size Reduction in Solid
Waste Processing: Progress Report 1973-1974, College of
Engineering, University of California—Berkeley, 1974.
Woodruff, K.L., Preprocessing of Municipal Solid Waste for Re-
source Recovery with a Trommel, National Center for Re-
source Recovery, Inc., Washington, D.C., February 1975.
GRAVITY SEPARATION
Bqettcher, R.A., Air Classification of Solid Wastes, U.S.
Environmental Protection Agency, Report No. SW-30c, 1972.
Chereirdsinoff, Paul N., "Air Classification of Solid Wastes,'1
Pollution Engineering, December 1974.
Degner, Vernon R. and McChesney, Bob, Performance of Advanced
RC Separator on Municipal Solid Waste, WEMCO Division,
Envirotech Corporation, Sacramento, 1974.
McChesney. Robert D.R. and Degner, Vernon R., Hydraulic,
Heavy Media and Froth Flotation Processes Applied to Re-
covery of Metals and Glass from Municipal Solid Waste
Streams, WEMCO Division, Envirotech Corporation,
Sacramento, 1974.
Michaels, E.L. et al., Heavy Media Separation of Aluminum
from Municipal Solid Waste, Institute of Mineral Research,
Houghton, Michigan, February 1974.
Pipeline Transport of Shredded Solid Waste, U.S. Environmental
Protection Agency Report No. SW-36c. of, 1971.
UNIT OPERATIONS
Arella, David G. and Garbe, Yvonne M., Mineral Recovery from
the Noncombustible Fraction of Municipal Solid Waste, U.S.
Environmental Protection Agency Report SW-82d.l, 1975.
Dicke, Carl H., "Control Systems for Furnaces," U.S. Patent
No. 2,335,263, Nov. 30, 1943.
Drobny, N.L. et al., Recovery and Utilization of Municipal
Solid Waste, Battelle Memorial Institute Columbus Labora-
tories, U.S. Environmental Protection Agency Report SW-lOc,
1971;
Engdahl, Richard B., Solid Waste Processing: A State-of-the-
Art Report on Unit Operations and Processes, Battelle
92
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Memorial Institute Columbus Laboratories, U.S. Environmental
Protection Agency Report SW-4c, 1969.
Spaite, Paul., "Refuse Disposal and Heat Recovery in Steam
Boilers," U.S. Patent No. 3,759,196, September 18, 1973.
WASTE MANAGEMENT REPORTS TO CONGRESS
Collection of Papers from Third Japan-United States Governmental
Conference on Solid Waste Management. Compiled by H.
Lanier Hickman, Jr., U.S. Environmental Protection Agency,
June 1976.
Compilation of Papers from Third National Congress Waste Manage-
ment Technology and Resource Recovery. Co-sponsored by
National Solid Wastes Management Association and the U.S.
Environmental Protection Agency, San Francisco, CA, Nov-
ember 14-15, 1974.
Darnay, Arsen J. Jr., Acting Deputy Assistant Administrator
for Solid Waste Management Programs, Environmental Pro-
tection Agency, Statement Before the Subcommittee on
Minerals, Materials and Fuels, Committee on Interior and
Insular Affairs, Unsited States Senate, Washington, DC,
October 30, 1973.
First Report to Congress, Resource Recovery and Source Re-
duction, prepared by the Office of Solid Waste Management
Programs, U.S. Environmental Protection Agency. 1974.
Second Report to Congress, Resource Recovery and Source Reduction,
prepared by the Office of Solid Waste Management Programs,
U.S. Environmental Protection Agency, 1975.
Third Report to Congress, Resource Recovery and Source Reduction,
prepared by the Office of Solid Waste Management Programs,
U.S. Environmental Protection Agency, 1975.
Report to Congress on Resource Recovery, U.S. Environmental
Protection Agency, February 22, 1973.
Report to Congress, Using Solid Waste to Conserve Resources
and to Create Energy/ by the Comptroller General of the
United States, February 27, 1975.
Report to Congress, Federal Materials Research and Development,
Modernizing Institutions and Management, by the Comptroller
General of the United States, December 2, 1975.
93
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Report to Congress, An Evaluation of Proposed Federal Assistance
for Financing Commercialization of Emerging Energy Tech-
nologies, EMD-76-10, by the Comptroller General of the
United States, August 24, 1976.
ECONOMICS OF WASTE MANAGEMENT
Abert, J.G., Alter, H., and Bernheisel, J.F., The Economics of
Resource Recovery from Municipal Solid Waste, National
Center for Resource Recovery, undated.
Alter, H., et al., Specifications for Materials Recovered from
Municipal Refuse, The National Center for Resource Recovery,
May 1975.
Darnay, A., and Franklin, W.E., Salvage Markets for Materials
in Solid Wastes, U.S. Environmental Protection Agency,
Cincinnati, 1972.
Hall, Jeffrey et al.. Development of an Economic Analytical
Framework for Solid Waste Policy Analysis, Environmental
Dynamics, Inc., EPA Report 600/5-75-014, September 1975.
Hopper, Richard E., A Nationwide Survey of Resource Recovery
Activities, U.S. Environmental Protection Agency, Washington,
D.C., January 1975.
Hopper, Richard, The Resource Recovery Industry, A Survey of the
Industry and Its Capacity, U.S. Environmental Protection
Agency, Cincinnati, 1976.
Kinderman, E.M., Economics of Solid Waste Recovery, Stanford
Research Institute, Stanford, CA, undated.
Levy, Steven, Markets and Technology for Recovering Energy
from Solid Waste, U.S. Environmental Protection Agency,
Washington, D.C., 1974.
Lowe, Robert A., Use of Solid Waste as a Fuel by Investor-Owned
Electric Utility Companies, Proceedings of the EPA/Edison
Electric Institute Meeting, July 1975.
Materials Needs and the Environment Today and Tomorrow, Final
Report of the National Commission on Materials Policy,-
June 1973.
Mikelich, Donald L., "Breakeven Economics of Resource Recovery
Systems," Proceedings of the Fifth Mineral Waste Utilization
Symposium, April 1976.
94
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Mineral Resources and the Environment, prepared by the Committee
on Mineral Resources and the Environment (COMRATE), Com-
mission on Natural Resources, National Research Council,
undated.
Mineral Resources and the Environment - Supplementary Report:
Resource Recovery from Municipal Solid Wastes, prepared by
the Committee on Mineral Resources and the Environment
(COMRATE) Commission on Natural Resources, National Resource
Council, 1975.
Ohio EPA Guide to Financing Solid Waste Management Systems in
Ohio, prepared by Division of Program Planning, Office of
Land Pollution Control, May 1976.
"Proposed New Power Plant Utilizing Solid Waste as Fuel," Cessna
Aircraft Company, Pawnee Division, Wichita, KS, March 12,
1974.
Renewable Resources for Industrial Materials, a report of the
Committee on Renewable Resources for Industrial Materials,
Board on Agriculture and Renewable Resources, Commission on
National Resources, National Research Council, undated.
Resource Recovery Plant Implementation, Guides for Municipal
Officials, U.S. Environmental Protection Agency, Washington,
D.C.
Resource Recovery from Mixed Municipal Solid Wastes: An
Examination, Analysis and Status Report, Physical and
Economic Resources Committee, Miami Valley Regional
Planning Commission, Dayton, OH, June 1975.
Shilepsky, Alan, Resource Recovery Plant Implementation: Guides
for Municipal Officials, Interim Report, U.S. Environmental
Protection Agency, Cincinnati, October 1975.
Smith, Frank A., Resource Recovery Plant Cost Estimates: A
Comparative Evaluation of Four Recent Dry-Shredding De-
signs, U.S. Environmental Protection Agency, Cincinnati,
July 1975.
Stearns, Robert P. and Davis, Robert H., "A New Look at the
Economics of Separate Refuse Collection," Waste Age, May/
June 1974.
GENERAL RESOURCE RECOVERY ARTICLES
Abert, J.G., and Zusman, Morris, "Resource Recovery: A New
Field for Technology Application," AIChE Journal, November
1972.
95
-------
Albrecht, Oscar W., "Shipping Wastes to Useful Places," Reprint-
ed in Environmental Science and Technology, May 1976.
Anon., "U.S. Finds a Rich Resource: The Nation's Trash Pile,"
U.S. News and World Report, May 1974.
Anon., "The Recycling Dream Is Turning Into Reality," Modern
Plastics, September 1972.
Available Information - Resource Recovery and Source Reduction,
U.S. Environmental Protection Agency, October 1974.
Bailie, Richard C., and Alpert, Seymour, "Conversion of
Municipal Waste to a Substitute Fuel," Public Works,
August, 1973.
Barnes, Richard, Evaluation of New Energy Sources for Process
Heating, Dow Chemical Company, September 1975.
Bechtel Corporation, Fuels from Municipal Refuse for Utilities,
March 1975.
Benziger, Jay B. et al., Resource Recovery Technology for Urban
Decision Makers, Columbia University, New York, January
1976.
"Biomass and Waste-Derived Fuels Handling and Preparation:
Market Potential, Technology Applications, and Business
Opportunities," Gorham International, Inc., Gorham, Maine,
undated.
Boyd, James, "A National Policy Toward Recycling," Reprint in
Environmental Science and Technology, May 1976.
Brown, Owen, "Energy Generation from Wood-Waste," presented at
the International District Heating Association, French Lick,
Indiana, June 1973.
Brown, Sam C., Refuse as a Source of Fuel for Power Generation
Electric Utility Industry Restraints, Virginia Electric
and Power Company, December 1973.
Brown, Sam C. Jr., "Refuse as a Source of Fuel for Power
Generation—Electric Utility Industry Restraints," Edison
Electric Institute Bulletin, Jan/Feb 1974, pp, 30-33.
Campbell, William J., "Metals in the Wastes we Burn," Reprint
in Environmental Science and Technology, May 1976.
Chantland, Arnold 0., "Make Kilowatts Out of Refuse," Reprint
from The American City, September 1974.
96
-------
Colonna, Robert A., Decision-Makers' Guide in Solid Waste
Management, U.S. Environmental Protection Agency,
Cincinnati, 1976.
Colonna, Robert A., and McLoren, Cynthia, Decision-Makers'
Guide in Solid Waste Management, U.S. Environmental Protec-
tion Agency, Cincinnati, 1974.
Combs, R.T., "Burning of Urban Waste in Utility Boilers," pre-
sented at the Virginia State Air Pollution Control Board,
Technical Advisory Committee Annual Meeting, May 1974.
Darnay, Arsen J. Jr., "Resource Recovery and Land Protection:
An Environmental Imperative," Solid Waste Management Pro-
gram, Environmental Protection Agency, May 1974, speech to
the Spring Meeting of Paperboard Group, API.
"Development of the Solid Waste Resource," Environmental Letters,
9(4) , 379-394 (1975) .
Dille, Earl K., Klumb, David L., and Sutterfield, G. Wayne,
"Recycling Solid Waste for Utility Fuel and Recovery of
Other Resources," Edison Electric Institute Bulletin,
Jan/Feb 1974, pp. 20-23.
Dille, Earl K., and Klumb, David L., "Solid Waste as a Source
of Fuel," presented at the International Pollution
Engineering Congress, Chicago, September 1974.
Dreifke, Gerald B., Klumb, David L., and Smith, Jerrel D.
"Solid Waste as a Utility Fuel," Proceedings of the Ameri-
can Power Conference, 1973, Vol. 35.
DuMond, T.C., "Gold in Them Thar Hills - of Refuse," Iron Age,
July 1974.
Environmental Letters, An International Journal for Rapid
Communication, ed. James W. Robinson, 1975.
EPA Press Briefing on Solid Waste Management and Energy,
February 1974.
"Evaluation, Extraction, and Recycling of Certain Solid Waste
Components," Great Lakes Research Institute, Erie,
Pennsylvania, 1972.
Ferguson, F.A., Morse, Park L., Miller, Katherine A., Refuse as
a Fuel for Utilities, Stanford Research Institute, Menlo
Park, CA.
Fernandes, J.H., "Using Waste Materials as Industrial Fuel," Re-
print in Plant Engineering, May 1975.
97
-------
Franklin, W.E., Bendersky, D., Shanon, L.J., and Park, W.R.,
Resource Recovery: Catalogue of Process, Midwest Research
Institute, Kansas City, MO, February 1973.
Ganotis, Chris, G., and Hopper, Richard E., "The Resource
Recovery Industry," reprint in Environmental Science and
Technology, May 1976.
Ganotis, Chris, and Hopper, Richard E., "The Resource Recovery
Industry," reprinted from Environmental Science and
Technology, May 1976.
Golueke, C.G., "Domestic Cellulose Waste," paper presented at
the NSF (RANN) special seminar "Cellulose as a Chemical
and Energy Source," University of California- Berkeley,
June 1974.
Grinstead, R.R., "Bottlenecks," Environment, April 1972.
Guide for Compiling a Comprehensive Emission Inventory, EPA,
Research Triangle Park, NC, June 1972.
Hale, Samuel Jr.,A Statement by the Deputy Assistant Admini-
strator for Solid Waste Management Programs Before the Sub-
committee on the Environment, Committee on Commerce,
U.S. Senate, June 1973.
Hale, Samuel, "The Federal Resource Recovery Demonstration
Program," reprint from Professional Engineer, June 1973.
Hawkins, Denise F., Resource Recovery Plant Implementation:
Guides for Municipal Officials Further Assistance, U.S.
Environmental Protection Agency, Cincinnati, 1975.
Hollander, Herbert I., and Lesslie, J. Dixon, "On-Site Disposal
of General Plant Waste and Energy Recovery."
"How Trash is Being Turned into Useful Heat," reprint from
Environmental Science and Technology, 1976.
Huang, C.J. et al., Energy Recovery from Solid Waste, Volume I -
Summary Report, University of Houston, April 1975.
Huang, C.J. et al., Energy Recovery from Solid Waste, Volume II •
Technical Report, University of Houston, April 1975.
"Improving Productivity in Solid Waste Collection," a brief for
elected officials, The National Commission on Productivity,
Washington, DC, USGPO 1974-757-139.
98
-------
Konopka, A.P., Systems Evaluation of Refuse as a Low Sulfur Fuel:
Part 3 - Air Pollution Aspects, Reprint from ASME publi-
cation and presented at the ASME Winter Meeting, Washington,
DC, November 28-December 2, 1971.
Kreiter, E.G., "Energy Recovery From Municipal and Industrial
Waste," Conservation and Recycling, Vol. 1, pp. 78-81
(1976) Pergamon Press.
Levy, Stephen, "Refuse as a Supplementary Fuel," presented at
the 3rd Annual Solid Waste Symposium, San Jose, CA,
March 1971.
Levy, Steven J. and Rigo, H. Gregor, Resource Recovery Imple-
mentation: Guides for Municipal Officials Technologies, U.S.
Environmental Protection Agency, Cincinnati, 1976.
Linde, Ronald K., "Solid Wastes, Geothermal Conversion Provide
Alternative Electric Power Sources," reprint in Professional
Engineer, November 1974.
Lingle, Stephen A., "Paper Recycling in the United States," U.S.
Environmental Protection Agency, printed in Waste Age,
November 1974.
Lischer, Vance C. Jr., "Solid Waste as Supplementary Boiler Fuel
for Paper Mills," Reprint in Tappi, June 1976.
Lowe, Robert A., Energy Recovery from Waste, Solid Waste as
Supplementary Fuel in Power Plant Boilers, U.S. Environ-
mental Protection Agency, Cincinnati, 1973.
Lowe, Robert A., Energy Conservation Through Improved Solid
Waste Management, U.S. Environmental Protection Agency,
Cincinnati, April 1974.
MacAdam, Walter K., "Megawatts from Municipal Waste," IEEE
Spectrum, November 1975.
Nuss, Guy et al., Base Line Forecasts of Resource Recovery, 1972
to 1990, Midwest Research Institute, Kansas City, MO,
March 1975.
Nydick, S.E., and Hurley, J.R., Study Program to Investigate Use
of Solid Waste as a Supplementary Fuel in Industrial Boil-
ers, Environmental Protection Agency, TE 4184-120-75,
May 15, 1975.
Peterson, Bob, "There's Gold in Your Garbage," reprinted by U.S.
Environmental Protection Agency from Scouting, 62(7):
46-48, 84-86, October 1974.
99
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"Plastic Challenge in Packaging: Disposability," reprint in
Modern Plastics, March 1970.
"Problems and Opportunities in Management of Combustible Solid
Wastes," International Research and Technology Corp. Report
No. EPA-670/2-73-056, August 1973.
"Putting Solid Waste and Resource Recovery in Perspective,"
National Center for Resource Recovery brochure.
Resource Recovery, The State of Technology. February 1973.
Resource Recovery and Conservation, An International Journal,
May 1975.
Resource Recovery from Solid Waste in Ohio, Final Report pre-
pared by Stanley Consultants, October 1976.
"Resource Recovery and Utilization," Proceedings of the National
Materials Conservation Symposium, National Bureau of
Standards, Gaithersburg, MD 29 April-1 May 1974, ASTM
Special Technical Publication 592.
Resource Recovery and Waste Reduction - A List of Current Re-
ports, U.S. Environmental Protection Agency, 1976.
Roberts, John J. and Lewis, Bradley, A., "Environmental
Pollution Associated with Refuse Combustion in Power Plants,"
Edison Electric Institute Bulletin, Jan/Feb 1974, pp. 23-26.
Roberts, R.M., and Wilson, E.M., Systems Evaluation of Refuse as
a Low Sulfur Fuel: Part I - The Value of Refuse Energy and
the Cost of Its Recovery, reprint from ASME publication and
presented at the ASME Winter Annual Meeting, Washington, DC,
November 28-December 2, 1971.
Roberts, R.M., et al., Systems Evaluation of Refuse as a Low
Sulfur Fuel - Vol. I, Envirogenics, Inc., Foster Wheeler
Corp., and Cottrell Environmental Systems, Inc., November
1971.
Roberts, R.M., et al., Systems Evaluation of Refuse as a Low
Sulfur Fuel - Vol. II - Appendices, Envirogenics Company,
Foster Wheeler Corp., and Cottrell Environmental Systems,
Inc., November 1971.
Schultz, H., and Walker, F.E., Characterizing Combustible
Portions of Urban Refuse for Potential Use as a Fuel, Bureau
of Mines Report of Investigations, 1975.
100
-------
Sheng, H.P., and Alter, H., "Energy Recovery from Municipal Solid
Waste and Method of Comparing Refuse-Derived Fuels," Resource
Recovery and Conservation, Elsevier Scientific Publishing
Co., 1975.
Shilepsky, Alan and Lowe, Robert A., Resource Recovery Implement-
ation: Guides for Municipal Officials Planning and Overview,
U.S. Environmental Protection Agency, Cincinnati, 1976.
Skinner, John H., The Demonstration of Systems for Recovering
Materials and Energy from Solid Waste, U.S. Environmental
Protection Agency, Cincinnati, 1974.
Solid Waste as Fuel for Power Plants, National Technical In-
formation Service, 1973.
"Solid Waste Project: Resource Recovery," Garbage Guide, No. 8
(1977) , newspaper published by the Environmental Action
Foundation, Washington, D.C.
Sommerlad, R.E., Bryers, R.W., Shenker, J.D., Systems
Evaluation of Refuse as a Low Sulfur Fuel: Part II - Steam
Generator Aspects, reprint from ASME publication and pre-
sented at the ASME Winter Annual Meeting, Washington, DC,
November 28-December 2, 1971.
Stanczyk, Martin H. et al., "Continuous Process for Mechanically
Separating Materials Contained in Urban Refuse," U.S. Patent
No. 8,848,813, November 19, 1974.
Stone, Ralph and Brown, David E., Forecasts of the Effects of
Air and Water Pollution Controls on Solid Waste Genera-
tion, Ralph Stone and Company, Los Angeles, CA,
December 1974.
Study of the Feasibility of Federal Procurement of Fuels Pro-
duced from Solid Waste, Arthur D. Little Co., U.S. Environ-
mental Protection Agency, Washington, DC, July 1975.
Support of Environmental Program Planning, Stanford Research
Institute, ONR-DARPA, October 1972.
Symposium - "Energy Recovery from Solid Waste," Journal of the
Washington Academy of Science, March 1976.
Tillman, David A., "Fuels from Recycling Systems," Reprint
Environmental Science and Technology, May 1975.
The Treatment and Management of Urban Solid Waste, Edited by
David Gordon Wilson, published by Technomic Publishing Co.,
Westport, CT.
101
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Tunnah, Barry G., Hakki, Adel, and Leonard, Roger J., Where the
Boilers Are, A Survey of Electric Utility Boilers with
Potential Capacity for Burning Solid Waste as Fuel, Gordon
Associates, Inc., New York, New York, 1974.
Wilson, E. Milton, and Freeman, Harry M., "Processing Energy
from Wastes," reprint in Environmental Science and Techno-
logy, May 1976.
AKRON
Glaus, Pyle, Schomer, Burns, and Dehaven, Inc., Architects and
Consulting Engineers, "Recycle Energy System for Akron,
Ohio," Akron, Ohio, February 19, 1973.
Glaus, Pyle, Schomer, Burns and DeHaven, Inc., Architects and
Consulting Engineers, "Recycle Energy Systems, Preliminary
Phase Report of Solid Waste Reduction Energy Recovery for
Akron, Ohio," Akron, Ohio, June 1974.
Glaus, Pyle, Schomer, Burns, and DeHaven, Inc., Architects and
Consulting Engineers, "Recycle Energy System, 1,000 Ton
Per Day Solid Waste Reduction Energy Recovery Project for
the City of Akron, Ohio," Akron, Ohio, March 13, 1975.
AMAX
Cordiano, Joseph J., Refuse as a Supplement to Coal Firing,
AMAX Resource Recovery Systems, Inc., Industrial Fuel Con-
ference, Purdue University, October 2-3, 1974.
Hecht, N.L., Duvall, D.S., Puckett, R.B., Wisemiller, J.P.,
Misel, H.E. Jr., and McClellan, J.L., Design for a Resource
Recovery Plant, prepared for AMAX, Inc., July 1974.
AMES, IOWA
City of Ames Supplementary Fuel Project, Solid Waste Inciner-
ation Study, Supplement to February 6 Report, April 24,
1976.
Hall, J.L., Joensen, A.W. and Shanks, H.R., Environmental
Effects of Solid Waste as a Supplemental Fuel, Ames Labora-
tory, USERDA, Iowa State University, March 1976.
Project Summary, City of Ames, Iowa, Solid Waste Recovery
System, May 3, 1974.
102
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Solid Waste Incineration Study, Fibbs, Hill, Durham and
Richardson, Inc., February 6, 1975.
BUREAU OF MINES
Fact Sheet: Edmonston (Md.) Solid Waste Recycling Project, U.S.
Department of the Interior, Bureau of Mines, undated.
Sullivan, P.M., Stanczyk, M.H., and Spendlove, M.J., Resource
Recovery from Raw Urban Refuse, College Park Metallurgy
Research Center, U.S. Department of the Interior, Bureau of
Mines, Report of Investigations 7760, 1973.
COLUMBUS, OHIO
City of Columbus Municipal Power System - Alternatives and
Analysis to the Year 2000 - a Report by the City of Columbus,
Ohio State University School of Administration Task Force,
August 1974.
Hogan, J.D., Roberts, K., Lasko, R., L'Esperance, W., Runde,
0., Schottenatein, M., and Thomas, J., Proposal of the
Columbus City Administration to Build a Solid Waste Fueled
Electric Power Generating Facility, Economic Policy Com-
mittee, Chamber of Commerce of Columbus, no date.
Vaughan, D.A. et al., "Environmental Effects of Utilizing Solid
Waste as a Supplementary Power Plant Fuel," Battelle
Columbus Laboratories, Columbus, Ohio, undated.
COMBUSTION EQUIPMENT ASSOCIATES - ECO FUEL
TM
Chemical and Electron Microscope Analysis of ECO-Fuel II
Combustion Equipment Associates, Inc., undated.
Combustion Equipment Associates, Inc., and Arthur D. Little,
Inc., Solid Waste Resource Recovery Plant, no date.
Combustion Equipment Associates sales brochures and Annual Re-
port for 1976.
Technical Evaluation of the Feasibility of Burning ECO-Fuel at
Philadelphia Naval Shipyard, Environment and Energy Systems
Division, CERL, January 1974.
103
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CONNECTICUT
A Plan of Solid Waste Management for Connecticut, prepared by
General Electric Company, Corporate Research and Development
in cooperation with the State of Connecticut, Department of
Environmental Protection, June 1973.
The Connecticut Solid Waste Management Program, Harvard Business
School, 1973.
C.P.U.
Combustion Power Company, Inc., report from J.A. Campbell, re-
ceived April 1973.
Combustion Power Unit-400: CPU-400, prepared by Combustion
Power Company, Inc., for the Bureau of Solid Waste Manage-
ment, 1969.
Dry Material Separation System description.
Wade, Gordon L., and Lam, Tai-Loy P., Fluidized Bed Combustion
of Municipal Solids, 165th ACS National Meeting, Dallas,
Texas, April 8-13, 1973.
FOSTER WHEELER CORPORATION - LIVINGSTON, N.J.
Sommerlad, R.E., European Experience - Solid Waste Fueled
Central Energy Conversion Plants, October 1973.
Systems Evaluation of Refuse as a Low Sulfur Fuel:
Part I Roberts, R.M. and Wilson, E.M., "The Value of
Refuse Energy and the Cost of Its Recovery"
Part II Sommerlad, R.E., Bryers, R.W., and Shenker, J.D.,
"Steam Generator Aspects"
Part III Konopka, A.P., "Air Pollution Aspects" presented
at the ASME Meetings, December 1971, Foster
Wheeler Company.
FRANKLIN
Hydrasposal Fibreclaim, Solid Waste Recycling and Resource
Recovery Plant, Franklin, Ohio.
Neff, N. Thomas, Solid Waste and Fiber Recovery Demonstration
Plant for the City of Franklin, Ohio, An Interim Report,
A.M. Kinney, Consulting Engineers, 1972.
104
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FT. WAYNE & G.M. - CUBETTES
Hollander, Herbert S., Polich, James W., and Cunningham, Newell
F.f Beneficiated Solid Waste Cubettes as Salvage Fuel for
Steam Generation, presented at Purdue University Industrial
Coal Conference, October 6-7, 1971.
National Recycling Corporation Report, October 1968.
Weston, Ray F., Community Solid Wastes Utilized as Salvage Fuel
Cubettes for Municipal Electric Generation, City of Fort
Wayne, Indiana, August 30, 1971.
NCRR
Engineering Feasibility Study Supplement, NCRR, May 1974.
Materials Recovery System, Engineering Feasibility Study, NCRR,
no date.
Regional Resource Recovery and Solid Waste Management Program,
New York Environmental Facilities Corp., November 1974.
Schilling, Robert D., CH2M Hill Capabilities, Resource and Re-
covery from Solid Waste.
NEW YORK
Christensen, H.F., Solid Wastes - Monroe County, N.Y. Style,
Rochester, New York.
EPA Solid Waste Task Force, Draft Summary Report Comprehensive
Solid Waste Management Plan for Refuse Disposal and Re-
covery of Material and Energy Resources, City of New York
Environmental Protection Administration, October 1975.
Horner and Shifrin, Consulting Engineers, Appraisal of Use
of Solid Waste as Supplementary Fuel for Utility Boilers,
1973.
ST. LOUIS - UNION ELECTRIC
Dille, E.K., Klumb, D.L., Sutterfield, G.W., Recycling Solid
Waste for Utility Fuel and Recovery of Other Resources, pre-
sented to 1973 Frontier of Power Technology.
105
-------
Dreifke, G.E., Klumb, D.L., Smith, J.D., Solid Waste as a
Utility Fuel, American Power Conference, 35th Annual Meet-
ing, May 1973.
Fact Sheet on Solid Waste Utilization System, Public Relations
Office, Union Electric Company, 1975.
Horner and Shifrin, Inc., Solid Waste as a Fuel for Power Plants,
Environmental Protection Agency, Solid Waste Management
Office, 1972.
Klumb, D.L., Union Electric Facilities for Burning Municipal Re-
fuse at the Meramec Power Plant, October 1972.
Klumb, D.L., and Brendel, Paul R., Resource Recovery from Solid
Waste, October 1, 1976.
Klumb, D.L., Brendel, P.R., Resource Recovery from Solid Waste:
The Story of Union Electric's Solid Waste Utilization
System, Union Electric Company, St. Louis, October 1976.
Lischer, Vance C. Jr., The Union Electric Solid Waste Utiliz-
ation Project, Ohio Valley Regional Conference of the Society
of American Military Engineers, Wright-Patterson Air Force
Base, Ohio, November 18, 1976.
Mullen, J.F., "Steam Generation from Solid Wastes: The
Connecticut Rationale Related to the St. Louis Experience,"
Combustion Engineering, Inc., Windsor, Connecticut, May
1974.
Shannon, L.J., Schrag, M.P., Honea, F.I., Bendersky, D., St.
Louis/Union Electric Refuse Firing Demonstration Air
Pollution Test Report, U.S. Environmental Protection Agency,
August 1974.
Shannon, L.J., Fiscus, D.E., Gorman, P.G., St. Louis Refuse
Processing Plant: Equipment, Facility, and Environmental
Evaluations, U.S. Environmental Protection Agency, May
1975.
Sutterfield, G.W., Refuse as a Supplementary Fuel for Power
Plants, U.S. Environmental Protection Agency, Interim Re-
port, July 1974.
Union Electric Company, A Progress Report for Engineers Employed
by Electric Utilities, Solid Waste Disposal Seminar,
October 1972.
Wisely, F.E., Sutterfield, G.W., Klumb, D.L., St. Louis Power
Plant to Burn City Refuse, Civil Engineering - ASCE, January
1971.
106
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TULSA, OKLAHOMA
"PSO Research Project: Waste as an Energy Source Study Set,"
The Tulsa Tribune, December 18, 1975.
Sales brochure, Williams Brothers Urban Ore, Inc.
"Sampling Garbage," The Tulsa Tribune, March 31, 1976.
"Tulsa Garbage May Be Used As Energy Source," Tulsa Daily World,
March 31, 1976.
OTHER RESOURCE RECOVERY PROJECTS
"An Urban Energy and Waste Reclamation System," IITRI Project
Suggestion 75-1050X, IIT Research Institute, Chicago, 1974.
Berkowitz, Lawrence, Solid Waste Separator Interim Progress Re-
port, The Franklin Institute Research Laboratories, Franklin,
Ohio, 1972.
Board of County Commissioners, Broward Company, Comprehensive
Solid Waste Management Study, June 1976.
Buonicore, A.J., and Waltz, J.P., District Heating with Refuse
Derived Fuel at Wright-Patterson Air Force Base, Dayton, OH,
September 1975.
"Computer System Fights Pure, Unadulterated Trash," Digital De-
sign News Reports, no date.
Elo and Rhodes, Inc., Consulting Engineers, "Solid Waste Pro-
cessing Plant - Palmer Plant," Easton-Palmer, Pennsylvania,
September 1974.
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Metropolitan Area Council of Governments, April 1974.
Holligan, James E. et al., Potential for Solid Waste as an
Energy Source in Texas, NTIS, November 1974.
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Ohio, submitted by American Can Company, Americology
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Facility, Lowell, MA, August 1974.
107
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Rigs, H.G., Use of Refuse as a Fuel at Fort Monmouth, New
Jersey. Construction Engineering Research Lab., April 1975.
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Operation, Economics, Grumman Ecosystems Corp., undated.
Smith, John W., "Solid Waste to Energy, Memphis Style," Herf
College of Engineering, Memphis State University, presented
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ference, University of Louisville, Kentucky, undated.
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System in the Tennessee Valley Authority Service Area, con-
ducted by the Tennessee Valley Authority, July 1976.
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Toftner, Richard O., Evaluation of the Ridgewood Army Weapons
Plant, Highlights Report, PEDCo-Environmental Specialists,
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CONFERENCES
Conversion of Refuse to Energy, First International Conference
and Technical Exhibition, Montreux, Switzerland,
November 3-5, 1975.
Proceedings of a Symposium on Solid Waste Demonstration Projects,
Cincinnati, May 4-6, 1971. Publication was compiled by
Patricia L. Stump.
Proceedings of 1968 National Incinerator Conference. Papers
presented at 1968 National Incinerator Conference, New
York, New York, May 5-8, 1968.
Proceedings of 1970 National Incinerator Conference. Papers
presented at 1970 National Incinerator Conference, Cincinnati,
Ohio, May 17-20, 1970.
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presented at 1972 National Incinerator Conference, New York,
New York, June 4-7, 1972.
108
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Proceedings of 1974 National Incinerator Conference. Papers pre-
sented at 1974 National Incinerator Conference, Miami,
Florida, May 12-15, 1974.
Proceedings of 1976 National Waste Processing Conference. Papers
presented at the 1976 National Waste Processing Conference,
Boston, Massachusetts, May 23-26, 1976.
Proceedings of the (First to Fifth) Mineral Waste Utilization
Symposium, U.S. Bureau of Mines and IIT Research Institute,
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March 4-5, 1971.
109
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
\ DEPORT NO.
EPA-600/7-78-143
3. RECIPIENT'S ACCESSIONING.
4. TITLE ANDSUBTITLE
INVESTIGATION OF ADVANCED THERMAL-CHEMICAL CONCEPTS FOR
OBTAINING IMPROVED MSW-DERIVED PRODUCTS
5. REPORT DATE
August 1978 (issuing Date)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
N.L. Hecht
D.S. Duvall
8. PERFORMING ORGANIZATION REPORT NO.
B.L. FOX
9. PERFORMING ORGANIZATION NAME AND ADDRESS
University of Dayton Research Institute
300 College Park Avenue
Dayton, Ohio 45469
10. PROGRAM ELEMENT NO.
1NE624
11. CONTRACT/GRANT NO.
R-804421-01
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory— Cin., OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES
Project Officer: Albert Klee (513) 684-7871
16. ABSTRACT
Although a number of resource recovery from refuse programs have been effective,
the quality of the products recovered could be enhanced to improve their marketability.
The purpose of this study was to investigate the potential of known processes that
could improve the quality of the fuels or other products derived from the organic
fraction in refuse.
Possible processes for improving the quality of products from the organic fractioi
derived from municipal solid waste (MSW) were determined, and descriptions were
developed for each process. An analytical framework for technical and economic
assessment was developed to serve as a guide for analysis. Major thermal and chemical
processes used in the pulp and paper, wood, textile, and resource recovery industries
were identified.
This study concentrated on those processes designed to produce a carbon char, a
powdered fuel, and liquid and gaseous fuels from the municipal solid waste. The
chemical and thermal treatments of most interest were the Worcester Polytechnic's
hydrogenation-liquefaction process, Wright-Malta's steam injection pyrolysis process,
and cellulose embrittlement.
Basic requirements were defined for producing a fine powdered fuel from the
organic faction of MSW. More quantitative measurements of the embrittlement process
| parameters are recommended.
1 /. l^tT W AND LJUOUMtlN 1 AINAl-Yblb
2. DESCRIPTORS
Liquefaction
Municipal Solid Waste
Pyrolysis
Refuse
13. DISTRIBUTION STATEMENT
Release to Public
b.lDENTIFIERS/OPEN ENDED TERMS
Carbon Char
Cellulose Embrittlement
Fuel
Hydrogenation
Resource Recovery
Solid Waste Management
19. SECURITY CLASS (This Report!
Unclassified
20. SECURITY CLASS (This page)
Unclassified
c. COSATI Field/Group
13B
21. NO. OF PAGES
118
22. PRICE
EPA Form 2220-1 (9-73)
110
. S. GOVERNMENT PRINTING OFFICE: 1978-757-140/1419 Region No. SHI
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