Catalytic Manganese Oxide Removal
Technology
Aneliese Ramsay and Alan Uraz
2013
Agenda
• Volatile Organic Compounds (VOC’s)
• Sick Building Syndrome: Reasons,
Reduction Methods, Stats
• Various technologies for removing
VOC’s currently used in the filter
market
• Catalytic technology
• Thermal catalytic filtration manganese
oxide
VOC’s
• Volatile Organic Compounds (VOCs)
in Your Home
• Volatile Organic Compounds (VOCs)
are chemicals that evaporate easily at
room temperature. The term
“organic” indicates that the
compounds contain carbon. VOC
exposures are often associated with
an odor while other times there is no
odor. Both can be harmful. There are
thousands of different VOCs produced
and used in our daily lives.
Many products emit or “off –gas”
VOCs.
VOC Concentrations
in a New and Old House
New houses have as much as ten times more VOCs than older houses.
New House
Old House
0.2 to 17.0 mg/m3
0.02 to 1.7 mg/m3
Source: Etkin, D., 1996, Practical advice for the control of indoor environmental
quality, Volatile Organic Compounds in Indoor Environments, Cutter Information
Corp., Arlington MA., pg. 70.
VOC Contaminants Found in Indoor Air in 41 Office
Buildings
Compounds
Average
Level (ppb)
Formaldehyde
Acetaldehyde
Benzene
Toluene
1,4-ichlorobenzene
Carbon Disulfide
Styrene
Butyl Acetate
xylene
Decane
Undecane
Acetone
Naphthalene
11.6
4.2
2.1
8.3
1.4
1.1
1.6
3.3
3.3
1.4
2.0
27.1
13.0
Number of Buildings
in which Compound
Found
Percentage
41
27
41
41
14
17
12
14
35
29
22
28
10
Source: Freihaut, J., Pennsylvania State University, College of Engineering, Department of
Architectural Engineering.
100%
66%
100%
100%
34%
42%
29%
34%
85%
70%
54%
68%
24%
VOC’s in Household Products
Carcinogens
Acetaldehyde
Benzene
2-butoxyethanol
1-chloro-2,3epoxypropane
Chloroform
Ethylbenzene
Formaldehyde
N-ethyl-N-nitrosoethanamine
Citrus-scrub
Comet disinfectant powder
Febreze air effects
Glance HC Glass and Multisurface cleaner
Goof Off cleaner
Pine-Sol brand cleaner
Pioneer Super cleaner
Shineline Seal Floor Sealer
Simple Green Concentrated
Cleaner/Degreaser/Deadorizer
Waxie 21 Glass Cleaner
Waxie Green Floor Finish
Reproductive Benzene
Toxins
Dibutyl phthalate
Ethoxyethanol
Toluene
Alpha HP Multi-Surface
Cleaner
Comet Disinfectant Powder
Goof off Cleaner
Shineline Seal Floor
Sealer/Finish
Hormone
Disruptors
Benzophenone
1-chloro-2,3epoxypropane
Dibutyl phthalate
Ethylene glycol
N,Ndimethylformamide
Nonlyphenol
ethoxylate
Phenol
styrene
3M Brand Glass Cleaner
Clorox Regular Bleach
Comet Disinfectant Powder
Glance HC Glass and MultiSurface Cleaner
Goof Off Cleaner
Shineline Seal Floor Sealer
Simple Green Concentrated
Cleaner
Twister
Waxie 21 Glass Cleaner
Neurotoxins
Acetone
3M Brand Bathroom Cleaner
Health Effects of VOCs
VOC > Inhalation
Health Effects
Acute
Household Cleaners
Eye irritation/ watering
Organic Solvents
Throat irritation
New Carpets
Headaches
New Furniture
Nausea /Vomiting
Fumes from Idling
automobiles in attached
garage
Dizziness
Chemicals stored in the
house
Recently applied adhesives
Asthma exacerbation
Chronic
Cancer
Liver Damage
Kidney Damage
Other Air Pollutants
Ozone
Central Nervous System
Damage
Source: Minnesota Department of Health, Indoor Air Program,
http://www.health.state.mn.us.divs/eh/indoorair/voc/
Formaldehyde
• Colorless, strong smelling gas
• Household products, glues, permanent
press fabrics, cosmetics
• Known to be a human carcinogen National
Toxicology Department June, 2011 12th
RoC
• Naturally occurring in the environment
VOCs -Formaldehyde
• The highest levels of airborne formaldehyde have been
detected in indoor air, were it is released from products
such as building materials and home furnishings.
• Formaldehyde levels range from 0.10 to 3.8 parts per
million (ppm) in homes.
• Formaldehyde has been detected in ambient air; the
average concentration reported in U.S. urban areas were
in the range of 1.1 to 20 parts per billion (ppb).
• Formaldehyde is a known carcinogen.
Source: U. S. Environmental Protection Agency, http;//www.epa.gov/ttn/atw/hlthef/formalde.html
Formaldehyde in the News
“Exposure to the widely used chemical formaldehyde may raise one's risk
of getting amyotrophic lateral sclerosis (ALS), or Lou Gehrig's disease, U.S.
April 16th 2008
researchers said on Wednesday”.
Formaldehyde spill closes school:
April 28th 2009
June 10th 2011
May 23rd 2010
“A school in Norfolk was evacuated and almost 900 pupils
were sent home when a fish preserved in a jar of formaldehyde
was dropped in a science laboratory.”
“Formaldehyde, styrene among substances deemed carcinogens or likely to
cause cancer. The substance was moved into the “known carcinogen” category
based on additional research that found those with higher exposure were at
increased risk for certain types of rare cancers, including cancer of the throat
and a cancer of white blood cells known as myeloid leukemia, officials said.”
China News Service states:
“This indoor pollution causes respiratory and other
conditions that kill 2.2 million youths each year, one
million of whom are under the age of five”
“Government scientists listed formaldehyde as a carcinogen, and
said it is found in worrisome quantities in plywood, particle board,
mortuaries and hair salons”
OHSA vs. Other Agencies
• PEL .75 ppm over 8
hours
• 2 ppm allowed for 15
min.
• NIOSH REL 0.016
ppm
• Ceiling limit of .1ppm
• ACGIH TLV .3 ppm
SBS- Overview, Reasons, and Stats
• Lets define Sick Building Syndrome
• Acute health effects (20% 2 weeks)
• Linked to time in a building
• Leave building symptoms reduced
Overview
•
•
•
•
•
History of SBS
It all began in the 1970’s
Legionella, air-tight buildings, energy crunch
Poor layout
Inappropriate furnishings and building fabric
An open office floor plan. Lack of
attention to the space planning
A typical building designed to be
air tight but there could be
unintended openings
Classifications
Building Related
Illness (BRI)
Internal Sources
Neurotoxic
Mass Psychogenic
Illness (MPI)
5 CFM, 10 CFM, 20
CFM
External Sources
Sources of SBS
Source Details
• Temperature- 20 degrees Celsius to 26
• Humidity- above 70%; less then 15% RH
• Ventilation- How well managed
• Artificial Light- lighting level, insufficient
contrast, excessive brightness and glare
• Noise and Vibrations- 70-80 dB. 32-128 Hz.
• Ions- and ozone
Source Details Continued
• Carbon Dioxide (C02)- p>0.05 positive
association. 350 ppm-2,500ppm study at
Carbon Monoxide (CO)- 10 mg/m3
• Nitrogen Dioxide (NO2)-.15 mg/m3 and
of .40 mg/m3 24 hour and 1 hour
SBS Stats
20% suffer headaches, mucus membrane
irritation, fatigue, dizziness, and nausea
20 million infected in the US from asthma
Americans spend 90% of their time indoors
6 million children
EPA estimates annual productivity losses to be
60 billion
50 to 80 percent of 900 workers in Britain,
Denmark, and Sweden report SBS
14% decrease in productivity
10 to 25 million workers in 800,00 to 1.2
million commercial buildings have SBS
3% decrease nationwide if multiplied by the
est. suffers of SBS
5% greater if air velocity decreased by 0.1 m
per second
4% lower when carbon dioxide decreased from
1000 to 600 ppm
3-6 billion could be saved due to reduced
allergies and asthma
Manganese Oxide
Formaldehyde Elimination
Catalysis
• Increase rate of a reaction, and are not consumed in
the reaction themselves.
• Significant use in industrial applications. Used in one
or more steps in 90% of manufactured products.
• Catalytic Converters
• NOx, hydrocarbons, carbon monoxide >>> N2 (nitrogen)
carbon dioxide, water
Manganese
•
•
•
•
•
Element
Transition Metal
Highly abundant element (12th most in Earth’s crust)
Exists in numerous crystal and oxidation states
MnOx- black/brown
MnOx Catalyst
• Black/brown
• Nanometer scale ( ~ 50 nm)
• Increases Surface Area to Volume Ratio (SA:V)
• Size of virus
• Increases amount of contact with air
• Commercial grade MnOx not nanometer scale
Thermal Catalytic Process
How the Thermal Catalytic Process Works
Nano-particle
Manganese Oxide
Harmless Water and
Carbon Dioxide
Mars and Van Krevelen
Mechanism
H2O
Langmuir-Hinshelwood
Mechanism
Eley-Rideal Mechanism
Formaldehyde
H2O
H2O
CO2
CO2
MnOx Catalyst
Benefits
• Destruction of Formaldehyde and some VOC’s
• Passive, works at room temperature, no additional
heating or UV element necessary
• Longevity
• Cheap
Limits on Formaldehyde
• California EPA Worker Safety Limit: 9 ppb
• Average for most homes and businesses: 17 ppb
• Carcinogen
• Used to preserve tissue permanently
• Widely used in carpeting, flooring, glues, resins, and woodbased furniture
• EPA estimates every 8 ppb of formaldehyde causes 1/10,000
people to have an increased risk of cancer = 60,000 people
Lawrence Berkeley National Laboratories
MnOx Catalyst
NaMnO4 + MnSO4 + H2O = MnO2 +H2SO4 + Na2SO4 +H2O
Performance:
80% single-pass formaldehyde destruction at 100 fpm, 30-45
ppb foraldehyde (CH2O)
-No byproducts (formate, CO, etc)
-3 months continuous operation
-20% drop in formaldehyde removal
Sidheswaran et al, 2011, Lawrence Berkeley National Laboratories
Filter Longevity
Slide Test Data
MnOx Single Pass Conversion Longevity Under Constant
200-300 ppb Formaldehyde Exposure
Conversion Efficiency
100.00%
90.00%
80.00%
70.00%
60.00%
50.00%
40.00%
30.00%
20.00%
10.00%
0.00%
0
50
100
Days
150
200
Wrapping it all Up
• VOC’s
• Sick Building Syndrome
• Formaldehyde
• Catalytic Technology
• Manganese Oxide
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