University of California, Riverside

University of California, Davis

Performance and Environmental

Impact Evaluations of Alternative
Waste Conversion Technologies in
California

Public Workshop
April 14, 2004

Center for Environmental Research and Technology

 University of California, Riverside
University of California, Davis

Introductions
California Integrated Waste Management Board
 Fernando Berton – Project Coordinator

UC Riverside, College of UC Davis, Department of

Engineering, Center for Biological and Agricultural
Environmental Research and Engineering
Technology (CE-CERT) Bryan Jenkins - Co-
Joseph Norbeck – Co-Principal Principal Investigator
Investigator Robert Williams –
Colin Hackett – Co-Principal Development Engineer
Investigator
Tom Durbin – Research Engineer
Bill Welch – Development
Engineer

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Overview
• CIWMB Background – Fernando Berton
• University of California Project Overview
– Tom Durbin
• Feedstocks – Tom Durbin, Rob Williams
• Processes and Products
– Tom Durbin, Rob Williams
• Environmental Impacts – Bill Welch
• Conclusions
– Tom Durbin, Rob Williams, Bill Welch
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University of California, Davis

Materials Being Landfilled

• 1989 legislation goal 50% diversion by 2000
(currently 47%)
• Organics (biogenic and fossil derived)
– Divert 10-13 million tons
– Landfill about 30 million tons
• Paper /cardboard largest category
– Recycle 4-5 million tons, Landfill 11 million tons

• Inorganic Components 8 million tons

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CIWMB Programs
• Dec 1999 Colloquy – Started Dialogue
• May 2001 Conversion Technology Forum
» Lack of political leadership
» Statutory constraints
» Lack of funding
» Economics and markets
» Lack of data
» Feedstock access
» Public perception & understanding
» Regulatory

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CIWMB Actions
• May 2001: Directed work in 5 areas:
– Interagency coordination
– Follow-up workshops/symposia
– Leveraging Fed/State $$
– Legislative proposal for small-scale grants and
lifecycle analysis research
– Assist applicants in permit process

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CIWMB Strategic Plan

• Conversion technologies could be major
tool towards zero waste
“…harnessing the energy potential in “waste” by using
new and clean technology to convert the material
directly into green fuel or gas to produce electricity.”

• Strategic Plan Goals & Objectives

– Environmentally preferable technologies
– Promoting new technologies and processes
– Alternative means of diversion, including
technologies that result in electricity and fuel

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CIWMB Policy Recommendations

• Adopted April 2002

• Conversion Technology Definition
• Conforming definition to “transformation”
• Findings
• Level of credit
• Regulatory and Permitting

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AB 2770 – Penultimate Version

• Administration-sponsored
• Definition, findings, level of credit
• Conforming changes for counting diversion
• Provisions on CEQA, testing residue, etc.
• R&D program
– Lifecycle costs/benefits
– Feedstock amenability with different technologies
– Small-scale grant/R&D program

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AB 2770 – Chaptered Version

• Gasification Definition
• Lifecycle and market impacts - RTI
• Technical evaluation: UC contract
• Risk assessment issues: OEHHA contract
• Report to Legislature

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 University of California, Riverside
University of California, Davis

Performance and Environmental

Impact Evaluations of Alternative
Waste Conversion Technologies
in California

University of California, Riverside

College of Engineering
Center for Environmental Research and Technology

University of California, Davis

Sponsored by:

California Integrated Waste Management Board

Center for Environmental Research and Technology
 University of California, Riverside
University of California, Davis

Technology Identification/Evaluation

• Definitions

• Analysis of performance characteristics

• Technical limitations

• Commercial status

• Types of feedstocks and quality

(moisture…)
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University of California, Davis

Processes Evaluated
• Thermochemical Processes
 Gasification
 Pyrolysis
 Catalytic Cracking
 Plasma Arc
• Biochemical Processes
 Fermentation
 Digestion
 Hydrolysis
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Product Evaluation
• Types of Products (e.g., electricity, fuels or
chemicals)
• Environmental impacts of products
• Processing steps
• Determine potential value of products that could
be produced from MSW [electricity & petroleum
equivalent]

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Environmental Impacts
• Emissions and emissions sensitivity to feedstocks

• Residues (hazardous and non-hazardous)

• Nuisance factors (noise, dust, traffic)

• Other environmental impacts

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Initial Work
University of California, Davis

• Initial work created a database (contract IWM-C0172 )

Report;
“Solid Waste Conversion: A review and database of current
and emerging technologies”

Interactive* Data Base is available at:

http://cbc1.engr.ucdavis.edu/conv/home.asp

* Including downloading of complete db

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Technical Survey
• Overall technical evaluation – vendors surveyed
but no evaluation of specific
technologies/vendors was performed
• Database of nearly 400 technologies/Vendors
 Initial UCD database, CIWMB database, Juniper
report, other sources
• About 70 responses received
 18 pyrolysis, 22 gasification, 11 biological, 10 plasma
arc, 9 catalytic cracking or other
 70% addressed survey questions
• Variety of systems and responses made it difficult
to make apples to apples comparisons
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Purpose of Workshop
• Present and explain preliminary findings

• Discuss potential advantages/liabilities of

alternative conversion technologies

• Provide a question and answer period

• Obtain feedback from stakeholders

• Discuss needs for additional

data/information Center for Environmental Research and Technology
 University of California, Riverside
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Project Timing
• Public Workshop – discuss preliminary findings
• Working Draft sent to Technical Advisory Board
 Comments expected by end of April
• Completed final draft reported by early May and
provided to Board for May meeting
 Posted on CIWMB website by early May
• Peer-review and public comments through late May
• Final report and responses to comments targeted for
completion by June for Board Review & approval
 Release of Final Report will be delayed to July
Board meeting if comments remain to be
addressed
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Feedstocks for Alternative

Conversion Technologies

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MSW & Diversion in California

• California landfills approximately 37.5 million tons of

waste annually (U.S. 231.9 million tons annually)
• 1990 Integrated Waste Management Act (AB 939) set
goals to cut waste disposal by 25 by 1995 and 50% by
2000
• Diversion Rates have increased considerably from 10%
in 1989 to 47% currently

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1999 Waste Stream

Characterization
Material Type Estimated % of
Waste Stream
Non-Organic 21%

Paper 30%

Plastic 9%

Lumber 5%

Other Organics 35%

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University of California, Riverside
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Waste Distribution
Mass/Energy
Mass Basis Energy Basis
50

45

40
Fraction of Total (%)

35

30

25

20

15

10

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Energy Equivalence
• 2370 MW of electrical power
 5% of states capacity and 6% of consumption
• 60 million barrels of crude oil
 @ $37 barrels ----- $2.2 billion

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Diversion Efforts for Misc. Organics

• 170 compost and Process facilities
• Composting, mulch, landfill cover, biomass to
energy
• Handle 6-7 million tons of organic materials
• 2 million wet tons (1.6 MBDT) urban wood
waste consumed in several of the state’s 30
biomass power plants
• Approximately 15 million wet tons (~ 8 MBDT)
of organics sent to landfill (C&D wood, green
waste, food waste, and ‘other’)

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Diversion Efforts for Paper

• Paper recycling represents 4-5 million tons (30-
35%)
• Cardboard boxes – recycle rate 52%
• Old newspaper – recycle rate 59%
• 10 million tons of paper to landfill
• 25 million tons of organic materials still sent to
landfill

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Diversion Efforts for Plastics

• Overall recycling rates for plastics are relatively
low and in the 2-4% recovery range
• PETE (soda bottle) recycling rates were over
70% in California in 1994 – up from 4% in 1988
• HDPE (milk jug) recycling rates were ~25%
nationally
• Recycling rates for plastic films and other plastics
which make up a predominant portion of the
waste remain below 3%, however

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Waste Reduction
• Packaging and containers
 32% of MSW generated, 28% of disposed MSW
• European Policies
 1994 EC Directive to take measures to reduce
package waste
 1991 German Extended Producer Responsibility
 Manufacturers take back container packaging
 Individual companies or central system
 US$2.25 per month
 Packaging 90% recovered and 80% recycled
• Uncertain how readily such programs could be
implemented in California
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MSW Combustion [aka incineration]

• 130 million tons worldwide at over 600 facilities
 Roughly 75% of waste in Japan
• 167 large facilities in US ---- 2/3rds on east coast
 3 in California
• Poor perception by public
 Incinerators have decreased emissions
considerably

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 University of California, Riverside
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Feedstocks for Alternative

Conversion Technologies
• Thermochemical processes can accept nearly all
organics
• Biochemical processes generally accept only
biodegradable feedstocks
 Some ‘high solids’ reactors can accept more
inhomogeneous waste – with the no
biodegradable components exiting as digestate
• Effects of metals in pigments, etc.
• PVC and chlorine containing materials can
contribute to dioxin/furan formation in
thermochemical processes Center for Environmental Research and Technology
University of California, Riverside
University of California, Davis

Waste Distribution
Mass/Energy
Mass Basis Energy Basis
50

45

40
Fraction of Total (%)

35

30

25

20

15

10

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 University of California, Riverside
University of California, Davis

Biochemical Process Feedstocks

• Biodegradable components of the landfill stream
include:
• Food wastes
• Leaves, grass, trimmings
• Paper/cardboard
• Wood waste
• Biodegradation varies in rate and degree

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Biochemical Process Feedstocks

• Biodegradation is not complete
• Lignin fraction will not degrade
anaerobically
Lignin amounts:
• Wood (20-30%)
• Food wastes (5-20%)
• Paper (1 – 25%)
• Practical systems can not completely
degrade the non-lignin components, due to
time, volume, energy, and expense Center for Environmental Research and Technology
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Biochemical Process Feedstocks

Biogas Potentials
• Laboratory studies to determine Biomethane
Potential (BMP)
• analogous to BOD assays for waste water

• Sample is digested under ideal AD conditions

until no more biogas is produced (4-8 weeks)

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Biochemical Process Feedstocks

Biomethane Potential (BMP) of some feedstocks
Energy in Biogas per wet pound of feedstock
CH4 Generated
(BTU/lb input)
Vegetable oil 16024
Office paper 5609
Corrugated paper 4389
MSW C 2586
MSW B 2466
MSW D 2387
Food waste 1969
MSW A 1918
Newspaper 1534
Branches 1519 Sources:
Chynoweth, et.al., (1993)
Grass 1161 Owens and Chynoweth (1993)
Blend of grass, leaves, branches 1130 Eleaser, et.al., (1997)
Tchobanoglous, et.al.., (1993)
Leaves 1123

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LCA/ Marketing study

• Examined impacts of alternative conversion
technologies on recycling
• Most of results related to additional
preprocessing needed for conversion technologies
• No effects on recycling of paper
• Plastics recycling would increase for biochemical
processes

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Recommendations
• Improve characterization of waste in conjunction
with waste characterization studies
• Proximate, ultimate, and elemental analysis
 Ash, metals, toxic congeners
• Higher heating values (HHV)
• Characterize protein, carbohydrates, and fats in
typical food wastes

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Alternative Conversion
Technologies – Processes
and Products

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Conversion Processes to Evaluate

•Thermochemical •Biochemical
Higher Temperature Lower Temperature
Higher Rate Lower Rate
Gasification Anaerobic Digestion
Pyrolysis Ethanol
Catalytic Cracking Fermentation
Plasma Arc Hydrolysis

• Physicochemical
 Biodiesel
 Distillation

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Post recycled MSW

Option 1 Option 2
Send to Landfill Send to CT

Pre-treatment
All Organics (as required)
Biodegradable Organics

Thermochemical Biochemical
Conversion Conversion

Digestate Residue
Producer Synthesis (includes lignin)
gas gas, and liquids Post treatment
and solids

Direct use
heat or power Products:
Digestate products:
generation Biogas
Fertilizer
Soil amendment Ethanol
Compost Chemicals

Products: Residue to landfill

Cogeneration Fuels and/or waste water
of heat and Chemicals treatment.
power Materials Air emissions

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Combustion
• Full Oxidation of fuel for production of heat at
elevated temps w/o generating commercially
useful intermediate gases, liquids, or solids.
• Referred to as Incineration.
• Flame temp: 1500 - 3000ºF
• Heat & mass transport, progressive pyrolysis,
gasification, ignition, & burning, with fluid flow.
• Usually employs excess oxidizer to ensure max.
fuel conversion
• Recoverable Heat is only useful product.

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Pyrolysis
• Thermally degrade material w/o the addition of any
air or oxygen
• Similar to gasification – can be optimized for the
production of fuel liquids (pyrolysis oils), with fewer
gaseous products (but leaves some carbon as char)
• Pyrolysis oil uses (after appropriate post treatment):
liquid fuels, chemicals, adhesives, and other products.
• A number of processes directly combust pyrolysis
gases, oils, and char
• Temp. range: 750-1500oF.

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Gasification
• Emphasis is to form energetic gaseous
products with fewer liquids / solids
residues
• Conversion via direct internal heating
provided by partial oxidation using
substoichiometric air or oxygen.
• Also indirect heating methods (externally
fired burners) or autothermal methods
(exothermic reducing reactions )
• Temp. Range: 1300 - 1500ºF.
• Utilizes a reactant Center for Environmental Research and Technology
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Process Parameters
• Product composition can be changed by temp, pressure,
speed of process, and rate of heat transfer.
• Lower temp./fast pyrolysis temps -- more liquid products
• High temperatures produce more gases
• Higher pressures can increase reaction rates/ +scalability
• Pyrolyzing/gasifying media can be varied by using
hydrogen and/or steam.
• Hydrogen
 Enhances chemical reduction processes
 Suppresses oxidation of carbon in feedstock
 Inhibits formation of dioxins and furans
• Water or steam
 Increase porosity of char-activated carbon (charcoal)
 Change the resultant gases and vapors.
 Can use lower temperatures but higher pressures than “dry”
processes.
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General Gasifier

GAS CLEAN-UP

CYCLONE

GASIFIER GAS
COOLER CLEAN SYNTHESIS OR
FLY ASH PRODUCER GAS

(FOR UTIILIZATION)

AIR, Steam, Pure

SOLID FUEL
oxygen, etc.
(MSW, Biomass, etc)

ASH AND
BED MATERIAL

Source: Carbona Coporation

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Gasification Schematic

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Gasifier (IGCC)

STEAM TO GAS CLEAN-UP

CLEAN PRODUCT GAS
HRSG
WATER
FROM
HRSG
CYCLONE

AIR
GASIFIER GAS GAS TURBINE
COOLER
FLY ASH

Turbine Exhaust
HEAT RECOVERY
SOLID FUEL STEAM
(MSW, Biomass, etc) GENERATOR
AIR
BOOSTER
BED COMPRESSOR
MATERIAL AIR
FROM GAS
COOLER
STACK
STEAM TO GAS
COOLER

ASH AND STEAM

BED TURBINE
MATERIAL

CONDENSER

Source: Carbona Coporation

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Other example (BRI)

Patent 5,821,111 (1998) Bioengineering Resources, Inc.

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Gas-Phase Products
• CO, H2, CH4, O2, N2, H20, CO2 + more minor species
• Majority of processes surveyed utilize post-
combustion of gaseous for electricity/heat production
• Post combustion of gaseous products will produce
products similar to those found in typical combustion
(NOx, CO, hydrocarbons, etc.)
• Easier to clean than typical combustion
 Exhaust volumes are smaller (less/no O2/air)
 Pyrolysis oil formation – 80%, less than 20% gases
 Low molecular weight species (CH4 power plants,
CH4 or H2 engines)
 Cl, SO2, metals scrubbed prior to combustion
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Synthesis Gas
• Mixture of CO and H2 that can be produced from a
variety of sources
• The use of different reactants and process conditions
in gasification allows the gas phase composition or
the CO and H2 ratio to be varied
• Can be used to produce fuels, chemical products,
feed gas for low temperature biochemical processes
• Direct process exhaust is essentially eliminated
• Synthesis gas should be scrubbed prior to secondary
processing

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Catalytic Cracking
• Pyrolysis with catalytic cracking of oils
• Utilized in oil refineries on polymeric wastes to
produce liquid fuels
• Plastic Energy, LLC is siting a facility in California
using same technology as Zabrze, Poland facility
(established in 1997)
• Ozmotech (Australia) installing similar facilities in
Spain and Australia

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Catalytic Cracking
Plastic Energy LLC Facility

• Planning to process waste plastics (numbers 2,4,5,

and 6).
• ~95% will be film plastics (resins 2 and 4 or HDPE
and LDPE)
• PVC and PET will be hand sorted at MRF

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Catalytic Cracking
Plastic Energy LLC Facility
• Baled plastic delivered from MRF
• Washed in mechanically stirred flotation tank (any
inadvertent PVC should sink)
• Cleaned plastic is melted ~ 365 ºF
• Flows to reactor and introduced to catalyst, heated to ~600 ºF
• Crude oil is formed which is distilled to gasoline and very
low sulfur diesel component
• Gasoline used onsite for process energy,
• Diesel product sold

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Catalytic Cracking
Plastic Energy LLC Facility

Shred Melt Reaction Distillation

Baled & clean plastic
Plastic plastic

Gas
Heat

Generator
Electricity Gasoline

Low Sulfur Diesel

Product

Source: Larry Buckle Plastic Energy, LLC

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Catalytic Cracking
Plastic Energy LLC Facility

Product Mass Gallons/ton Gallons/da Gallons/

(%) feedstock y (50 t/day) day (100
t/day)

Diesel 85 242 12,100 24,200

Gasoline 14 45 2,250 4,500
Light 1 (vapor)
hydrocarbons

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Plasma Arc Systems

• Heating Technique using electrical arc
• Developed for treating hazardous feedstocks
• Contaminated soils
• Low-level radioactive waste
• Medical waste
• Used in some metals processing
• Good for creating molten ash (slag), so is used for
incinerator ash melting and stabilizing in Japan
• One Commercial scale facility for treating MSW in Japan

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 Can
•University
University be used
of California, Riverside
of California, Davis

in pyrolysis,
gasification, Plasma Arc Systems
or
combustion
systems
– Depends on
amount of
reactive
oxygen or
hydrogen fed
to reactor
• Air or inert
gas is passed
through
electric arc
creating
ionized
plasma
• The plasma
can reach Center for Environmental Research and Technology
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Plasma Arc Systems

RCL Plasma – Recoverable Energy Estimates
No air/oxygen used in gasifier

Electricity production Technology

Energy at Gas furnace Gas turbine
exit of Reciprocating engine
Units (20% conversion Combined Cycle
(35% conv. efficiency)
gasifier efficiency) (45% conv. efficiency)

(MMBTU) 9726 1945 3237 4099

Less Electricity to power
Torch (MMBTU) -1895 -1895 -1895
Electricity for Export (kWh)
16 434 712
Net efficiency to
electricity (%) 0.5 14.3 23.5
Power Export-
(500t/day input) MWe 0.34 9 15

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Plasma Arc Systems

• Hitachi Metals/Westinghouse Plasma
• Commercial scale plant at Utashinai Japan
• 200 tons per day feed input
• ~50% is MSW
• ~50% Auto shredder residue (ASR)
• Energy for Plasma torches is less because
• ASR is more energetic fuel
• Operates with air injection to reactor in amount ~ 40%
of stoichiometric requirements
• This is a ‘plasma assisted’ air blown gasifier

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Plasma Arc Systems

Utashinai Plant Emissions
(reported by Westinghouse Plasma)

Compound Units Amount

Dioxin ng-TEQ /(Nm3) < 0.01

SO2 ppm <20

HCl ppm <30

NOx ppm <50 (catalyst

present)
Particulate g/(Nm3) <0.01
matter

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Thermochemical Products
• Fuel gases
 Internal/external combustion engines
 Fuel cells
 Other prime movers
• Liquid Fuels
 Methanol
 Fischer-Tropsch (FT) liquids
 Hydrogen
 Synthetic ethanol

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Thermochemical Products
• Chemicals
 Ethylene (recycling of plastics)
 Ammonia based fertilizers
 Substitute petroleum products
 Adhesives and resins
 Food flavorings
 Pharmaceuticals
 Fragrances
• Gas phase components for Biochemical
Processes

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Pyrolysis Oils
• Complex mixtures of hydrocarbons
 Alcohols, aldehydes, ketones, esters, water, etc
• Can be combusted on site in boilers and engines
 Lower heating values depending on feedstock
• Chemical uses
 Phenol species, acetaldehyde, formaldehyde, aromatic
chemicals
 Wood waste – fragrances, adhesives, resins, food
flavorings, pharmaceuticals
• Dioxins and Furans can concentrate in pyrolytic oils
 80-90% of total dioxins/furans
 Scrubbing 99.84% in removal of Cl prior to
condensation
 Still examining some data in this area
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Commercial Status
• Thermochemical processes more widely applied
to MSW in Europe and Japan

• Large-Scale thermochemical processes used since

the 1800s

• Many techniques developed for coal processing

 TyssenKrupp Uhde has ~100 gasifiers most for coal

• Most Waste facilities operate below 200 tons per

day
 Some will have higher capacity
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Commercial Status II
• SVZ facility at Schwarze Pumpe in Germany
 one of the largest facilities
 450k tpy solid waste & 55 tpy liquid waste.
• Mitsui & Takuma (licensees Siemens gasif. +
pyrolysis)
 Plants operating since 1990s, others planned or
constructed.
• Nippon Steel
 Dozen plants 80 to 450 tpd, most operational.
 Two plants 100 and 450 tpd capacities since late
1970s.
• Ebara/Alstom
 450 tpd facility in place. Center for Environmental Research and Technology
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Commercial Status III

• A number of Identified Plants did have issues in
commissioning, operating or financially
• Brightstar
• Fürth, Germany plant had accident
 Siemens abandoned the European market
• Karlsruhe, Germany facility - Thermoselect

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Pre-Conclusions -Thermochemical
• Pyrolysis/gasification appears to be technically
viable for electricity production
• Recommend CIWMB further investigate/evaluate
processes using synthesis gas for fuel or chemical
production where post combustion is not required
• Use of thermochemical processes seems to be
expanding but process validation is important
• Suggest AB2770 definition for gasification be
modified to be more scientifically correct
• Did not examine costs

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Biochemical Conversion

• Biochemical conversion-
– lower temperature and slower rates compared to
thermochemical methods
– Generally, higher moisture feedstocks are preferred
– Biodegradable components only
» ~None of the current waste plastic stream
» Lignin components of biomass are not degradable
anaerobically

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Biochemical Conversion

• Aerobic (with oxygen)

– Composting operates primarily in this mode
– Stabilizes/degrades material faster than if Anaerobic
– Only biochemical mode for lignin degradation (and is very
slow)

• Anaerobic (without Oxygen)

– Principal biological process occurring in landfills

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Biochemical Conversion

• Anaerobic decomposition
– Biodegradable material only (lignin does not degrade
anaerobically)
– Polymer carbohydrate needs to be broken up into
simpler molecules (sugars). Hydrolysis accomplishes
this
– Facultative and Fermentive bacteria/yeasts produce
» Biogas (~ 50-65% methane, balance CO2, + small
amounts of impurities): Anaerobic Digestion - AD
» Ethanol (and/or other chemicals): Fermentation

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Biochemical Conversion
• Fermentation route to ethanol and other
chemicals
– For sugars and starches is fully commercial (wine,
beer, corn (grain) derived ethanol)
– Not yet commercial for cellulosic biomass (most
MSW biomass is cellulosic)
» Because of expense and difficulty of Hydrolysis
» Must Hydrolyze cellulose/hemicellulose to sugars
and organic acids
» Then yeast ferments the sugars

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Biochemical Conversion
• Hydrolysis Methods
– Hydrothermal
» Hot water, maybe high pressure
» Steam or Ammonia explosion
– Enzymatic
» Cellulase enzymes to de-polymerize the cellulose
» Currently expensive but believed to be most economical route
in future
» Intensive research and engineering of microbes ongoing in
public and private institutions world wide
– Acid
» Dilute or Concentrated – Technologically mature
» Currently more economical than enzymatic

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Concentrated Acid Hydrolysis

Feedstock Size Concentrated H2SO4
Reduction Water

1st Stage 2nd Stage

Cellulose Hydrolysis Hydrolysis
Decrystallization

Steam/
Lignin
Electricity
Acid/sugar
separation Generation

Acid Sugars Ethanol

Reconcentration
Concentration

Water Fermentor
Neutralization/
Detoxification Gypsum

Source: http://www.ott.doe.gov/biofuels/concentrated.html)

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Biochemicals (fermentative route)

Source: Arkenol

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Fermentation
After Hydrolysis

Carbohydrate + Cell mass → Ethanol + CO2 +

More cell mass

Under best circumstances, mass yield of Ethanol

is 51% of mass of input carbohydrate
Accounting for microbe cell growth, best yield in
practical systems is ~ 46% (mass basis)

Recall, the lignin component does not participate

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Fermentation of components of MSW

Companies;
• Using Hydrolysis to yield sugars and organic
acids
– Masada
– Arkenol
– Waste to Energy (Genahol)
– And others
• Using Thermal gasification to depolymerize the
cellulose
– BRI
– Novahol
– And others?

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Masada ‘OxyNol’
• Middletown, N.Y., Permitted (start construction?)

Unit operations include

• MRF
• Feedstock Preparation (shredding and drying)
• Acid Hydrolysis Unit (single stage)
• Fermentation and Distillation Units
• Focusing on MSW feedstocks

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Masada ‘OxyNol’
Middletown Facility
• 230,000 tons per year MSW
• 70,000 dry tons per year Biosolids

Products
• Ethanol (25 -35 gallons per wet ton feedstock)
• CO2
• Recyclables (from up-front separation)
• Gypsum

“majority of revenue stream for a typical OxyNol facility

comes from tipping fee, not products produced from
waste”

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Arkenol
• Develops Biorefineries
• Cellulose to ethanol via concentrated acid
hydrolysis (2-stage)
• Commercial scale plant in Japan using waste
wood feedstock

• 67 gallons ethanol per dry ton of feedstock

(~equivalent to Masada yield on wet basis)

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Waste to Energy w/ Genahol

• 2-Stage Dilute Acid
Hydrolysis
• Brelsford Engineering
Proc.
• Attempting validation
plant in Santa Maria, CA
• MRF residue
– Biomass to ethanol
– Lignin & Plastics thermal
CT for heat and power
• Expect Similar Yields

Anaerobic digestion block diagram

Source: Brelsford Engineering, Inc

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BRI Energy, LLC

• Bioreactor ferments waste and synthesis gases
– Ethanol
– Hydrogen
• Proposing to gasify biomass and other
components in MSW and fermenting the
producer gas to ethanol

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BRI Energy, LLC

Source: patent 5,821,111 (Gaddy, 1998). Bioengineering Resources, Inc

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BRI Energy, LLC

• Yield from biomass feedstock is potentially
greater than acid/enzymatic hydrolysis because
lignin is converted in gasifier (Claim 75 gallons
ethanol/dry ton)
• Because of bacteria and bioreactor
characteristics, fermentation stage is quick
• Claim material is gasified and fermented to
ethanol in less than 1 hour. (Std. sugar
fermentation ~ 36-48 hrs.)
• Plastics, tires, waste oils can be processed to
ethanol in this system

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Novahol
• Also promoting ethanol from fermentation of
synthesis gas

• Focusing on wood waste right now (wood from

bark beetle infestation)

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Anaerobic Digestion producing Biogas

• Principle process occurring in Landfills

• Many waste water treatment plants use AD
• Extensive development and use of this
technology in Europe
– Policies; GHG reduction, Total Organic
Carbon restrictions in Landfill stream.

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Anaerobic Digestion Block Diagram

Particulate Organic Material

HYDROLYSIS

Sugars, Amino acids, Organic acids

ACETOGENESIS

Acetate, Hydrogen

METHANOGENESIS

Methane
CO2

* Adapted from Mata-Alvarez, J. (2003)]

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Anaerobic Digestion producing Biogas

• Systems can be classified;

– Low or High Total Solids
LS< 15% TS or > 85% moisture (‘wet’ systems)
HS range between 20-30% TS or 70-80% moisture (‘dry’ systems)
– Single Stage digester
– Two or multi-stages
– Batch
• Optimum Temperatures
– Mesophilic (85 – 95 ºF)
» Slower reaction – longer retention times
– Thermophilic (~120- 150 ºF)
» Faster but requires more heat energy

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Single Stage Low Solids AD (Waasa Process)

Biogenic
fraction of PULPING METHANIZATION
MSW Bioga
Pre- s
Chamber 10-15% TS

DEWATERING
Inoculation
Heat
loop
addition
Composting
Make-up
water Heavies Recycle process water Water
treatment

Hydrolysis, acetogenesis, and methanogenesis occur in a single vessel.

* Adapted from Mata-Alvarez, J. (2003)]

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Single Stage – High Solids Reactors

Biogas Biogas
Biogas

Inoculum
loop
Feed Digested
paste
Biogas
Feed
recirculation
Digested provides
Digested paste
paste Feed inoculant

Dranco Kompogas Valorga

Less pre-treatment, though high solids pumps cost

more
Some systems can accept Unsorted MSW (requires
some size reduction and removal of large items) –
though yield suffers * Adapted from Mata-Alvarez, J. (2003)]

‘Plug Flow’ reactors, therefore require method to

inoculate fresh feed Center for Environmental Research and Technology
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2-Stage AD Schematic
STAGE 1 STAGE 2
(hydrolysis) (methanogenesis)
Biogas
Solid Note: 2nd Stage could be
Feed reactor type;
CSTR,
Make-up UASB,
water Liquid Recycle Fixed Film,
(among others)
Dewatering
Waste and Water
Treatment
Liquid
(and/ or compost and
liquid fertilizer)
Composting

Opportunity to optimize hydrolysis and methane

production separately
First Stage can be Low or High Solids, continuous
or batch loading * Adapted from Mata-Alvarez, J. (2003)]
Second stage is generally Low Solids

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Anaerobic Phased-Solids Digester

High Solids Hydrolysis stages operate in Batch Mode;

Timing is phased for uniform methane production rate
Second stage is generally Low Solids
Best with source separated biogenic fraction of MSW
Source: Professor Ruihong Zhang

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Anaerobic Phased-Solids Digester

Model results for lab-scale APS digester
10
Total
Methane Production (L/day)
8

H-I H-II H-III H-IV

4

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Time (Days)

Methane production due to individual phased

batch hydrolysis reactors.
Overall methane production is smoother.
This system is being piloted.

Source: Karl Hartman, UCD

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AD in Europe

• 86 facilities larger than 3300 ton per year capacity

• Total installed capacity of 2.8 million tons waste per
year
• Spain will be treating 7% of biodegradable
components of MSW by end of 2004 (13 facilities,
average 70,000 tons per year).

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AD Capacity in Europe
Solid Waste Anaerobic Digester Capacity in Europe
3.0

2.5
Capacity (million tons/y)

2.0

1.5

1.0

0.5

0.0
1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004*

Facilities with > 10% of feedstock coming from MSW

*Data were projected for 2004
components.
Many co-feed with animal manures, biosolids De Baere, L. (2003).

~90% of capacity is composed of Single Stage systems

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Biochemical Process
Conversion Number of
Company Name Corp. Headquarters Process Type
Name Facilities
Kompogas Glattbrugg, Switzerland Kompogas AD 25
Valorga Montpellier, France Valorga AD 13
Organic Waste Systems Gent, Belgium Dranco AD 13
CiTec Finland/Sweden Waasa AD 11
BTA (Canada Composting Munich, Germany BTA AD
in North America) (Ontario, Canada) 10
Wright Environmental Ontario, Canada In vessel Composting 6
Mngmt.
Linde-KCA-Dresden Dresden, Germany AD & composting
(MBT) 3
Eco Tec Finland WABIO AD 3
Arkenol Ethanol via Acid
Hydrolysis 1
Arrow Ecology Haifa, Israel Arrow Bio AD 1
Wehrle Werk AG Emmendingen, Germany Biopercolat AD ?
U-plus Umweltservice Ettlingen, Germany ISKA MBT / AD ?
Onsite Power Systems Camarillo, CA APS (UC Davis) AD Pilot &
Proposed
Masada Resource Group Birmingham, Alabama CES Oxynol Ethanol via Acid Pilot &
Hydrolysis Proposed
WTE (w/ Genahol) Santa Maria, CA Genahol/BEI Ethanol via Acid
Hydrolysis Proposed

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Biochemical Conversion
Pre-Conclusions
• Technically viable for some components of waste
stream
• Costs (and perhaps low public awareness)
impede development

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Alternative Conversion
Technologies –
Environmental Impacts

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Present Situation
• Landfills produce mainly CH4, CO2
• Trace gas constituents (BTX, H2S, vinyl chloride)
• Landfills largest source of GHG methane
emissions --- roughly 1/3rd of total
• 3,000 landfills in California, 311 active
• 51 convert gas to energy currently –211 MW
• Another 26 planning to use energy – 29 MW
• 70 landfills flare landfill gas (66 MW eq.)
• Remainder (164) vent to atmosphere (31 MW
eq.)

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Thermochemical Process Emissions

• Intermediate gases/oils may contain CO, VOCs,
HCl, H2S, dioxins/furans
• Many processes surveyed use intermediate gas
combustion for electricity/heat production
• Post combustion of gaseous products will
produce products similar to those found in typical
combustion (NOx, CO, hydrocarbons, etc.)
• Easier to clean than typical combustion
 Intermediate gas volumes are smaller (less/no
O2/air)
 Low molecular weight species (CO, H2, CH4)
 Cl, S, PM can be scrubbed prior to combustion
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Dioxin/Furans I

Cl Cl
O

Cl Cl
O

Cl Cl

Cl
Cl O

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Dioxin/Furans-Formation II
• Poor gas-phase mixing
• Low combustion temperatures
• Oxygen-starved conditions
• Temperatures 480ºF to 1290ºF
• Formation from Wastes
 Feedstocks with high levels of Cl and Cu
 Oxygen content of feedstock 25-45%

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Dioxin/Furans-Studies
• Weber and Sakurai, Chemosphere, 45, 1111-1117
 Industrial Light Shredder (5% Cl) & Refrigerator
shredder (1% Cl), w/ 3-6% Cu
 90% PCDD/F in pyrolysis oils (1,500-10,000 ng/g)
• Mohr et al., Chemosphere, 34, 1053-1064
 Feedstock contained chloro-benzenes, phenols, PCBs
 PCDD/F 1,983 ng/g in oil for 3,485 ng/g feedstock
• Miranda et al., Polymer Degrad & Stability
 Vol. 73, pp 47-67, 2001
 Commingled plastics with PVC (7.9%)
 Cl volatilized at 680 ºF to HCl
 NaOH scrubber removed 99.84%
 Resulting pyrolysis oil contained 12 ppm Cl
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Pollution Controls
• Cold-quenching – dioxins/furans, acid gases
• Baghouse, ESP – particulate matter
• Catalytic/thermal incineration - dioxins/furans,
VOCs, CO
• Flame temperature control/catalytic reduction –
NOx
• Scrubber – Acid gases
• Carbon filters, carbon injection, duct sorbent
injection – dioxins/furans, VOCs

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Improvements in Air Pollution

Control
Emissions from Large MSW Incinerators

Pollutant 1990 2000 Percent

Emissions Emissions Reduction
Dioxins/Furans, total mass basis 218,000 g/yr 679 g/yr 99+
Dioxins/Furans, Toxic equivalent 4,260 g/yr 12.0 g/yr 99+
quantity basis
Mercury 45.2 tpy 2.20 tpy 95.1
Cadmium 4.75 tpy 0.333 tpy 93.0
Lead 52.1 tpy 4.76 tpy 90.9
Particulate Matter 6,930 tpy 707 tpy 89.8
Hydrochloric Acid 46,900 tpy 2,672 tpy 94.3
SO2 30,700 tpy 4,076 tpy 86.7
NOx 56,400 tpy 46,500 tpy 17.6
Source: United States Environmental Protection Agency Memorandum, “Emission from Large MWC
Units at MACT Compliance,” June 20, 2002

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Emissions Data
Emission Results for Various Pyrolysis/Gasification Facilities/Technologies (mg/Nm 3
unless noted)
PM NOx CO TOC VOC SO2 H2S Dioxins/furan HCl HF
(ng/Nm3)
Balboa Pacific 68 ppm 36 9 13 6
Brightstar 1.6-10 40-96 440-625 0.05 <0.1 <2 0.0331 <1.0 0.59
GEM 3 262 8 6 79 0.02 4 ND
Organic Power 3 168 5 5 8 0.07 5 0.2
PKA 2.3 54 38 2.3 7.7 0.02 2.3 0.15
Pyromex 135 38 0.5 20 0.005 1 0.03
RCR-Thermsave 183 8 6 41 0.02 4 0
RGR Ambient 3.6 75 6.1 3.4 7.7 6.3 0.23
Serpac 4.2-5.2 61-189 0.5-2.5 0.2-0.5 0.0-5.6 0.002 1.7-5 <0.1
Technip 3 180 10 2 5 0.001 5 0.2
Thermoselect 0.0007-
0.0011
Thide-Eddith 470 50 <15 <200 30 <1
TPS 3-7 200-300 2.5-5 5-15 0.013 0.6-2 <0.1

Notes: PM = particulate matter, TOC=total organic carbon, VOC=volatile organic

carbon, ND=not detect

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Emissions Data II

Metal Gaseous Emissions Results for Various Pyrolysis/ Gasification

Facilities/Technologies (mg/Nm 3 unless noted)
As Cd Cr Cu Pb Mn Hg All /other
metals
Brightstar 0.0051 <0.0002 0.013 0.0051 0.0080 0.072
GEM ND ND 0.07
Organic Power 0.004 0.03
PKA 0.002 0.002 0.07
Pyromex 0.002 0.07
RCR-Thermsave ND ND 0.07
RGR Ambient 0.016 0.35
Serpac 0.05
Technip 0.02 0.02 0.2
TPS <0.004 0.005 0.008-0.05

Notes: As=Arsenic, Cd = Cadmium, Cr=Chromium, Pb=Lead, Hg=Mercury, ND=not

detect

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Solid Waste Data

Ash Residuals and Leaching Data for Various Pyrolysis/ Gasification Facilities/Technologies (mg/l unless noted)
Units As Ba Cd CN Cr Cu Pb Mn Ni Hg Zn All
metals
BalPac mg/l 0.05 0.37 0.1 0.01 0.58
Compact m/kg 4 0.1 289
Power
Ebara/Alstom mg/l <0.001 <0.01 <0.005 0.056 0.013 <0.01 <0.0005 0.05
(glass
granulate)
GEM ppm <100 <100 1330 406 <100 109 <100
Nexus mg/kg <1 <0.05 <0.05 <1 <0.05
PKA mg/l 0.002 <0.001 <0.005 <0.01 0.072 0.014 <0.002 0.014
Notes: As=Arsenic, Ba=Barium, Cd = Cadmium, CN=Cyanide, Cr=Chromium, Cu=Copper, Pb=Lead,
Mn=Manganese, Ni=Nickel, Hg=Mercury, Zn=Zinc, ND=not detect

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Environmental Impact Summary

• All waste disposal methods carry environmental
risks
• Proper design of waste conversion processes must
address air emissions, liquid and solid residues
• Characterization and pre-sorting of feedstocks
can reduce emissions
• Process and pollution control technologies can
minimize environmental impacts, but must be
carefully designed and operated
• Overall environmental impacts of well-designed
alternative waste conversion technologies are
equal to or less than current practice of landfilling
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Conclusions for Alternative

Conversion Technologies

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Problem at Hand?
• Non-sustainable environment of landfilling of 37
million tons of material annually

• Landfill gas impacts & other factors

• Landfill expansion becoming more difficult and

not beneficial to society

• Source reduction, recycling, alternative

conversion technologies

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Available Feedstocks
• 2370 MWe or 60 million barrels of oil
• Paper and Cardboard
 Landfill 10 million tons, Recycle 4-5 million tons (30%)
 44% of energy value
• Plastics
 2nd high energy content – 30% of total
 11% of landfilled mass and 22% of landfilled volume
 Growing rapidly and recycling rates are relatively low
 Only thermochemical can process
• Biochemical Feedstocks
 Food waste
 Green/paper waste
• Contaminants
 Chlorine containing materials (PVC)
 Pigments in paper, other metal contaminants

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Thermochemical Processes
• Pyrolysis - Thermally degrade material w/o the addition of any air or
oxygen
 Can be used to maximize oil production
 Many processes use post-combustion for electricity
• Gasification - Conversion via direct internal heating provided by partial
oxidation using substoichiometric air or oxygen (Hydrogen or steam)
 Indirect heating methods (externally fired burners) or autothermal methods
(exothermic reducing reactions )
 Can be utilized to produce synthesis gases
• Synthesis gas produce chemical/fuel without combustion
• Combust for electricity -produce gaseous products similar to
combustion
 Lower exhaust volumes
 Lower molecular weight species
 Scrubbing prior to full combustion or use in chemicals/fuels

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Thermochemical Processes II
• Have the greatest potential to process the whole MSW
organic stream
• More commercial in Japan and Europe
• Some plants have experienced problems – Technology must
be proven sound
• Study did not cover economic viability
• Suggest AB2770 definition for gasification be modified to
be more scientifically correct
• More formal vendor should be conducted
• Need to consider possibility of fuels/chemical instead of
electricity – perhaps work in this direction
Synthetic ethanol, F-T diesel, hydrogen
Ethylene, fertilizers, petroleum products, adhesive
Pyrolysis Oils – fragrances, adhesives, resins, Pharmaceuticals
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Biochemical Processes
• Fermentation, anaerobic & aerobic digestion

• Carried out at lower temps. & reaction rates

• Utilize biodegradable feedstocks

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Environmental Conclusions
• Air Emissions – Thermochemical process
– Can use synthesis gas for fuel/chemical w/o
combustion
– Post-combustion – similar products to combustion
– Little for no oxygen/air – reducing environment
– Small air volume
– Low molecular weight species – cleaner to combust
– Less costly but similar emissions control
• Solid Waste
– Thermochemical processes concentrate but do not
create metallic species
• Liquid Waste
– Spent acids from biochemical processes, spent
scrubber solutions
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Socio-economic Impacts
• Full Life Cycle Analysis should be used in
comparing benefits/liabilities
• Potential Resource – 60 million barrels oil or
2370 MW electrical power
• Provide diversity of product markets
• Extension of landfills
• Impacts on recycling
• Environmental impacts

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Recommendations
• Formal vendor evaluation
• Improve Characterization of MSW
 Elemental analysis, heating value, biochemical properties
• Improve estimates of waste generation
• Collect emissions data for Thermochemical
• Investigate legislation for further increase in
landfill diversion
• Co-fund alternative conversion projects
• Study future landfill costs
• Study the feasibility of “zero waste” through
recycling or source reduction

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