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Introduction
The Volatile Organic Compounds (VOC) Recovery Seminar was held September 16 -17, 1998, in
Cincinnati, Ohio. The seminar was cosponsored by the U.S. Environmental Protection Agency's
(EPA's) National Risk Management Research Laboratory (NRMRL), the U. S. Department ofEnergy
(DOE), the American Institute of Chemical Engineers (AIChE), and the AIChE-affiliated Center for
Waste Reduction Technologies (CWRT). Representatives from industry, academia, consulting firms,
and government attended.
The purpose of the seminar was to bring researchers, technology developers, and industry
representatives together to discuss recovery technologies and techniques for VOCs. The seminar
focused on the specific VOC recovery needs of industry and on case studies that summarize effective
VOC product recovery techniques applicable to air, water, and solid waste. The case studies
highlighted examples in which existing and new recovery technologies resulted in significant cost
savings to industry.
The seminar focused on the following key issues:
Status and future direction of EPA, DOE, and other major research programs.
What are the latest technology innovations in VOC treatment and recovery?
* Performance and cost effectiveness of VOC recovery techniques.
How are recovery techniques applied to air, water, and solid wastes?
Presenters were from industry, academia, EPA, and various consulting firms. The presentations were
followed by several facilitated breakout sessions; these sessions allowed participants an opportunity
to discuss their needs and opinions on VOC recovery trends, research, and other issues.
This document contains hard copies of the overhead, slide, and computer presentations made during
the VOC Recovery Seminar. This document was developed as an aid when viewing the seminar
video and may serve as a backup in the event that the visibility of a slide, overhead, etc., is poor.
The document was produced using copies of slides, overheads, etc., provided by the speakers before
the seminar. In some cases, the speakers reordered and/or modified their presentation materials
during the seminar (e.g., new slides were used); these changes are not reflected in this document.
Also, no attempts were made to correct any typographical errors or misspellings.
Presentation materials are organized according to the seminar agenda located at the beginning of this
document. There were eight sessions during the seminar; presentation materials from different
sessions are separated using colored sheets containing the title of the session, the speakers' names,
and the presentation titles.
Finally, this document has not been subjected to the U.S. EPA's peer and administrative review; it
is intended merely as an aid when viewing the seminar video. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use.
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I
1
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DAILY AGENDA
VOC RECOVERY SEMINAR
SEPTEMBER 16-17, 1998
SPONSORED BY USEPA, USDOE, AIChE, AND CWRT
Day 1 - Wednesday, September 16,1998
8:00 AM Registration
8:30AM Session 1, Session Chair - Scott Hedges, USEPA, National Risk Management Research
Laboratory
Welcome and Introduction of Participants (Hugh McKinnon, USEPA, Associate Director for
Health, National Risk Management Research Laboratory)
Purpose of Seminar / Need for VOC Recovery (Subhas Sikdar, USEPA, Director Sustainable
Technology Division, National Risk Management Research Laboratory)
Definitions for Volatile Organic Compounds, Sources of VOCs, What is Recoverable? (Carlos
Nunez, USEPA, National Risk Management Research Laboratory)
Overview of VOC Recovery Technologies (Kamalesh Sirkar, New Jersey Institute of
Technology)
9:45AM Session 2 - Summary of VOC Recovery Research Programs, Session Chair - Stephen
Adler, Center for Waste Reduction Technologies
Industrial Research Programs (Ed Moretti, Baker Environmental)
DOE Research Programs (Charlie Russomanno, Office of Industrial Technologies, USDOE)
VOC Recovery Research at EPA-ORD (Teresa Harten, USEPA, Chief, Clean Products and
Processes Branch, National Risk Management Research Laboratory)
10:15AM Break
10:45AM Session 3 - VOC Recovery Technologies Applicable to Air Streams
(Group A), Session Chair - Philip Schmidt, University of Texas at Austin
Short Flow Path Pressure Swing Adsorption - Method for Lower Cost Adsorption Processing
SHERPA (William Asher, SRI International)
Solvent Recovery Applications at 3M (James Carmaker, 3M Corporation)
11:30AM Lunch
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DAILY AGENDA
VOC RECOVERY SEMINAR
SEPTEMBER 16-17,1998
SPONSORED BY USEPA, USDOE, AIChE, AND CWRT
Day 1 - Wednesday, September 16,1998
12:30PM Session 4 - VOC Recovery Economics and Technologies Applicable to Air Streams
(Group B), Session Chair - Joseph Enneking, NUCON International, Inc.
Economics of VOC Recovery: Using the OAQPS Cost Manual as a Tool for Choosing the
Right Reduction Strategy (Dan Mussatti, USEPA, Office of Air Quality Planning and
Standards)
Rotary Concentration and Carbon Fiber (Ajay Gupta, Durr Environmental)
Zeolite Absorption and Non-CFC Refrigeration - Condensorb (Jon Kostyzak, M&W
Industries)
A Novel Fiuidized Bed Concentrator System for Solvent Recovery of High Volume, Low
Concentration VOC-laden Emissions (Edward Biedell, REECO)
Recovery of VOCs by Microwave Regeneration of Adsorbents (Philip Schmidt, University of
Texas at Austin)
2:30PM Break
3:OOPM Session 5 - VOC Recovery Technologies Applicable to Air Streams (Group C), Session
Chair - Edward Biedell, REECO
Removal and Recovery of Volatile Organic Compounds from Gas Streams (Hans Wijmans,
Membrane Technology and Research, Inc.)
Synthetic Adsorbents in Liquid Phase and Vapor Phase Applications (Steve Billingsley,
Ameripure, Division of American Purification, Inc.)
Cryogenic Condensation for VOC Control and Recovery (Robert Zeiss, BOC Gases)
Brayton Cycle Systems for Solvent Recovery (Joseph Enneking, NUCON International, Inc.)
4:30PM End of Day 1
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DAILY AGENDA
VOC RECOVERY SEMINAR
SEPTEMBER 16-17,1998
SPONSORED BY USEPA, USDOE, AIChE, AND CWRT
Day 2 - Thursday, September 17,1998
8:30AM Session 6 - VOC Recovery Technologies Applicable to Aqueous Streams, Session Chair -
Kamalesh Sirkar, New Jersey Institute of Technology
Recovery of VOCs in Refinery Wastewater (Mike Worrall, AMCEC, Inc)
Separation of Volatile Organic Compounds from Water by Pervaporation (Richard Baker,
Membrane Technology and Research, Inc.)
Dehydration and VOC Separation by Pervaporation for Remediation Fluid Recycling (Leland
Vane, USEPA, National Risk Management Research Laboratory)
Polymeric Resins for VOC Removal from Aqueous Systems (Yoram Cohen, University of
California, Los Angeles)
10:OOAM Break
10:30AM Session 7 - VOC Recovery Tools/Techniques, Session Chair - Yoram Cohen, University
of California, Los Angeles
The New CPAS Separation Technology and Pollution Prevention Information Tool (Robert
Patty, The Construction Productivity Institute)
Comparative Cost Studies (Ed Moretti, Baker Environmental)
Availability of Technology Information, Including Internet-Based Sources (Heriberto Cabezas,
USEPA, National Risk Management Research Laboratory)
Techniques to Improve the Recoverability of VOC Streams - Air Flow Management, VOC
Concentrations (Charles Darvin,USEPA, National Risk Management Research Laboratory)
12:OOPM Lunch
1:15PM Session 8 - Trends/Issues/Research Needs by Industry - Facilitated Break-out Sessions,
Session Chair - Joseph Rogers, Center for Waste Reduction Technologies
3:OOPM Break
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DAILY AGENDA
VOC RECOVERY SEMINAR
SEPTEMBER 16-17,1998
SPONSORED BY USEPA, USDOE, AlChE, AND CWRT
Day 2 - Thursday, September 17,1998
3:15PM Session 9 - Results and Conclusions, Session Chair - Scott Hedges, USEPA, National
Risk Management Research Laboratory
Presentation of Break-out Session Results
Summary and Concluding Remarks / Seminar Follow-up (Scott Hedges, USEPA, National
Risk Management Research Laboratory)
4:15PM Adjourn
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RISK MANAGEMENT : STRATEGIC ISSUES
FOR VOCS IN THE ENVIRONMENT
Subhas K. Sikdar
Director
Sustainable Technology Division
National Risk Management Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
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Risk Management Strategic Issues for
VOCs in the Environment
Outline
What emissions data tell us
Industry Sources of Emission
Where are the problems most evident
Strategies for Reducing Risks
-------
Toxic VOCs in the Environment
Most emissions are anthropogenic
Most contaminated media are dilute in VOCs
Air and Water contamination is major health
and eco risk
- Organics : Tropospheric Ozone
Ozone Depletion
Lung Disease
Cancer Risk
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Toxics Release Inventory ( TRI) Data
TRI data allowed a comprehensive view
of pollution and helped in strategic
decisions for its reduction
- 33/50 program on 17 chemicals
- Project XL (site-specific)
- Common Sense Initiative (sector-specific )
TRI data created an awareness by
industry and citizens of the seriousness of
the pollution issue
- Company-specific emission reduction program
- Responsible care in chemical industry
- Pollution Prevention Concepts
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Top Chemicals with Largest
Production-related Waste (1998)
1998 Projected Change
Industry emission, mlbs 1996 -1998,%
Chemicals 10,711 + 6.8
Primary metals 4,157 - 2.0
Petroleum 2,149 0.0
Paper 1,607 - 0.5
Food 728 + 83.1
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Top Chemicals with Largest Production-related Waste (1996)
Release, Recycled,
Chemical mlbs mlbs
Methanol 245 555
Zinc Compounds 209 320
Ammonia 193 346
Nitrate Compounds 169 109
Toluene 126 995
Xylenes 88 156
Chlorine 67 83
HC1 66 159
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Three strategies for Reducing Risks
1. Remediation of Contaminated Media : after the fact
2. Control Technologies : treating pollution as it happens
3. Pollution Prevention : changing materials and processes
a. Substitution, avoidance, process changes
b. Recycle / reuse of materials
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Examples of Management Strategies
Remediation:
Land or ground water contamination
with Organics : Bioremediation,
Extraction followed by Destruction
Control:
VOC Emissions : incineration,
catalytic oxidation
-------
Examples of Management Strategies
Pollution Prevention :
Substitution / Process Changes
- Use of aqueous in place of chlorinated hydrocarbons
- Oxidation reactions without the use of chlorine
(Green Chemistry)
Recycle / Reuse
- Recovery of methylene chloride from polycarbonate
manufacture
- Recovery of solvents from paint spray booths
- In-process recycling of reactants / byproducts /
solvents for reuse in process
-------
Concluding Points :
All three strategic avenues are important for
VOC management
for VOC removal / capture, or recovery / reuse,
conventional technologies are inefficient
Technical Challenge : Highly efficient, cost
effective recovery methods would be needed
- Low-cost designer solvents with
high capacity
- High volume reduction methods
(e.g. pervaporation)
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ft * ^lj ^^\, " *
ง'^S'K lill^^s i 1^'^^'^^.lfoltJ^
iciui v/.rgame
Carlos IVl Nunez
U.S. Environmental Protection Agency
National Risk Management Research Laboratory
Air Pollution Prevention and Control Division
Research Triangle Park, North Carolina
September 16-17, 1998
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Definitions
Major VOC Sources
Considerations for Product Recovery
Volatile Organic Compounds (VOCs)
"Any compound of carbon, excluding carbon monoxide, carbon
dioxide, carbonic acid, metallic carbides or carbonates, and
ammonium carbonate, which participates in atmospheric
photochemical reactions"
Organic compounds with negligible photochemical reactivity are
excluded
Exemption petitions for 15 compounds
All VOCs are considered equal
2-3
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Negligibly Reactive
Four compounds were originally classified Negligibly Reactive
(methane, ethane, methyl chloroform, and Freon I ! 3)
Ethane is used as the standard cutoff (compounds with reactivities
below ethane might be considered for Exemption)
Since 1977 > 42 compounds or classes of compounds have been
classified Negligibly Reactive and added to the Exempt list
Most Exemptions determined using kOH value [reaction rate constant
for the reaction of a compound with OH (hydroxyl) radical], expressed
in units of cubic centimeters/molecule-second, and compared to the
kOH value of ethane
In 1993, EPA began receiving Exemption Petitions based on the
Maximum Incremental Reactivity (MIR), the grams ozone produced per
gram of compound reacted (acetone was first compound evaluated for
Exemption using MIR)
Non-Road Vehicles
Storage & Transport
Miscellaneous
Other
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1996 level represents total estimated reductions of
7% and 38% from 1995 and 1970 levels,
respectively
Significant emissions reduction in the mobile sector
due to uniform nationwide controls
Emission rate reduced to ~ 90% compensating for growth in
vehicle miles traveled (VMT), which more than doubled since
1970, and population
VOCs from natural sources almost equal to
anthropogenic emissions
CONSIDERATIONS FOR PRODUCT
RECOVERY
Technical Feasibility
Recovery efficiency (regulatory requirement]
Product quality (process requirement)
Product's physical and chemical characteristics
- Vapor pressure
- Molecular weight
- Polarity/Solubility
- Molecule size
Emission stream characteristics
Flow rate
Concentration
Temperature
Moisture
Contaminants
6-7
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CONSIDERATIONS FOR PRODUCT
RECOVERY (cont.)
Economic Feasibility
Identify capital and operating costs
* Recovery
Destruction
New
Compare annualized cost ($/unit of material recovered) to
virgin material cost and the cost of other treatment or disposal
It is economically feasible if recovery costs < disposal or
destruction and makeup material costs
CONSIDERATIONS FOR PRODUCT
RECOVERY (cont.)
Environmental
Requirements
Corporate
Requirements
Economics
8-9
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OVERVIEW
OF
VOC RECOVERY TECHNOLOGIES
Kamalesh K. Sirkar
Department of Chemical Engineering, Chemistry
and Environmental Science
New Jersey Institute of Technology
Newark,NJ 07102
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Selected References
1. S.D. Barnicki and J.R. Fair, "Separation system synthesis: a knowledge-based
approach. 1 & 2, lad. Eng. Chem. Res., 29, 421 (1990) and 31, 1679 (1992).
2. J.R. Graham and M. Ramaratnam, "Recover VOCs using activated carbon," Chem.
Eng., 6-12, February (1993).
3. J.L. Humphrey and G.E. Keller II, "Separation Process Technology," McGraw Hill,
New York, Chapter 7 (1997).
4. Y-L Hwang et al., "Steam stripping for removal of organic pollutants from water.
I & II," Ind. Eng. Chem. Res., 31, 1753-1759 and 1759-1768 (1992).
5. N. Mukhopadhyay and E.C. Moretti, "Current and potential future industrial
practices for reducing and controlling volatile organic compounds," CWRT, AlChE
(1993).
6. Papers Presented in "Zero Discharge Manufacturing: Removal of Organics from Air
I, II, III," Sessions 26,27 and 28. Preprints of Topical Conference on Sep. Sci. and
Tech., AlChE Annual Mtg., Part II, Los Angeles, CA, Nov. 16-21 (1997).
7. E.N. Ruddy and L.A. Carroll, "Select the best VOC control strategy," Chem. Eng.
Prog., 28-35, July (1993).
8. U.S. Environmental Protection Agency, "EPA Hanbook: Control Technologies for
Hazardous Air Pollutants," US EPA, Office of Research and Development,
Washington, DC, EPA/625/6-91/014, June (1991).
9. "Vapor Collection and Control Options for Storage and Transfer Operations in the
Petroleum Industry," API Publication 2557,1st Ed., American Petroleum Institute,
Washington, DC (1993).
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VOC (VOLATILE ORGANIC COMPOUNDS)
ORGANIC CHEMICAL HAVING A VAPOR PRESSURE 0.1 mm Hg
(At 20ฐC and 760 mm Hg)
PARTICIPATES IN ATMOSPHERIC PHOTOCHEMICAL REACTIONS
EXCLUDE CO, C02, H2CO3, METALLIC CARBIDES OR CARBONATES,
(NH4)2C03
MANY ORGANIC COMPOUNDS ARE VOCs (318 +)
ANNUAL VOC EMISSIONS FROM STATIONARY SOURCES
8.5-17 MILLION METRIC TONS/YR.
I I
450 - 900 TRILLION BTU/YR. 0.45 - 0.9 QUAD/YR.
(~ 3% OF TOTAL NET USAGE OF US INDUSTRY)
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CWRT STUDY BY MUKHQPADHYAY & MORETTI
1. PROCESS VENTS, WASTEWATER OPERATIONS, STORAGE TANKS,
TRANSFER OPERATIONS, AIR-STRIPPING OPERATIONS, PURGE
STREAMS, DEVOLATILIZATION OPERATIONS - MACT STANDARDS
2. REDUCTION OF ALIPHATIC, AROMATIC AND HALOGENATED
HYDROCARBONS; ALSO ALCOHOLS, ETHERS, GLYCOLS, ETC.
3. 40% CAP. EXPENDITURE FOR STREAMS , 500 SCFM
80% CAP. EXPENDITURE FOR STREAMS , 5,000 SCFM
by USERS
4. 90% CAP. EXPENDITURE FOR VOC STREAMS > 500-10,000 ppm <
50% CAP. EXPENDITURE FOR VOC STREAMS > 1,000-5,000 ppm <
8% CAP. EXPENDITURE LEAN VOC STREAMS < 500 ppm
by USERS
5. ADSORBERS (40% OF TOTAL SALES)
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VOC RECOVERY TECHNOLOGIES
1. GASEOUS STREAMS (AIR/N2)
(IN SOME TECHNOLOGIES, AQUEOUS STREAMS ARE PRODUCED AND
TREATED)
SOURCES OF POLLUTION IN A PLANT TOO NUMEROUS FOR
COLLECTION AND TREATMENT BY A CENTRAL FACILITY
2. LIQUID STREAMS
(IN SOME TECHNOLOGIES, GASEOUS STREAMS ARE PRODUCED AND
TREATED)
SOURCES OF POLLUTION MAY BE NUMEROUS BUT STREAMS
STILL COLLECTED OFTEN FOR CENTRAL CLEANUP
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BASIC PRINCIPLES BEHIND VOC RECOVERY PROCESSES
GASEOUS STREAMS
PHASE CHANGE PROCESSES; DISTILLATION, CONDENSATION
MASS SEPARATING AGENT-BASED PROCESSES;
A. EQUILIBRIUM-BASED PROCESSES: ADSORPTION, ABSORPTION
(ALSO MEMBRANE-BASED ABSORPTION)
B. RATE-GOVERNED MEMBRANE PROCESSES: VAPOR PERMEATION
MOST PROCESSES ARE HYBRID PROCESSES CONSISTING OF AT LEAST
TWO SEPARATION TECHNIQUES
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BASIC PRINCIPLES BEHIND VOC RECOVERY PROCESSES
AQUEOUS STREAMS
PHASE CHANGE PROCESSES; DISTILLATION
MASS SEPARATING AGENT-BASED PROCESSES
A. EQUILIBRIUM-BASED PROCESSES: ADSORPTION, STRIPPING,
MICELLAR SOLUBILIZATION
B. RATE-GOVERNED MEMBRANE PROCESSES: PERVAPORATION,
REVERSE OSMOSIS
FILTRATION PROCESSES; MEUF (MICELLAR ENHANCED
ULTRAFILTRATION)
MOST PROCESSES ARE HYBRID PROCESSES CONSISTING OF AT LEAST
TWO SEPARATION TECHNIQUES
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VOC RECOVERY BY A COMBINATION OF SEVERAL PROCESSES
Wastewater inlel
Counter-
current
air stripper
RH-modification unit
RH>80%
AA
Clean water out
X
Chiller
VOC stream
RH<50%
Stripped
condensate
Water- Q+*.I~A
saturated Stopped ,
VOC condensateT
stream '
*
tl
Steam *
Carbon
adsorbers
_
it
T
Steam
f Clean gas vented
J from system
Recycle loop for stripping air or nitrogen
Stripping agent
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Nitrogen -
purge gas
Propylene-nitrogen
vent gas
Purge
bin
Polymer
product
Membrane
modules
^^^-^^^
Nitrogen stream,
96% nitrogen
* Hydrocarbon stream,
recycle to reactor
VOC RECOVERY AND RECYCLE BY A SINGLE PROCESS
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ADSORPTION PROCESSES
METHODS OF REGENERATION
A. THERMAL REGENERATION:
1. ONSITE/OFF-SITE, STEAM, HOT N2 (450ฐF-BOC-AIRCO), MICROWAVE,
INFRARED FOR FIXED BEDS
2. ROTARY WHEELS (TRAVELLING BED), FLUIDIZED BEDS
B. PRESSURE SWING ADSORPTION (PSA)
C. PURGE GAS
TYPES OF ADSORBENT
1. ACTIVATED CARBON: EXCELLENT ADSORPTION, REGENERATION
PROBLEMATIC, CHEMICAL REACTIVITY (BED FIRES FROM KETONES,
ALDEHYDES, ETC.) POOR STABILITY, HUMIDITY CONTROL
2. SYNTHETIC RESIN BEADS: STYRENE-DIVINYLBENZENE POLYMERS,
SOLVENT-SWOLLEN FIRST AND THEN CROSSLINKED
3. ZEOLITES
4. AEROGELS
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Air to
Atmosphere Steam
Adsorption
Feed
Desorption
Distillation
Column
Surge Tank
Condenser
Blower
Pump
Acetone
(To Sales)
' Water
to Waste
Treatment
Fixed-bed adsorption process for recovery of acetone from air.
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Air from
outside
Heater
Desorbed gas
(concentrated)
Unclean air to be treated
Motor
Adsorbent wheel with monolithic adsorbent.
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POLYADฎ PROCESS
CONTINUOUS FLUIDIZED BED PROCESS
SEPARATE ADSORBER AND DESORBER: PNEUMATIC TRANSPORTATION
OF ADSORBENT PARTICLES
MACROPOROUS POLYMERIC PELLETS - BONOPORE - HIGHLY ABRASION
RESISTANT
STEAM-HEATED AIR-BASED DESORPTION - COOLING WATER USED FOR
VOC CONDENSATION
AIR FLOW RATES ~ 35000 m3/hr (500 - 500,000 nvVhr RANGE)
CHEMATUR ENGG., KARLSKOGA, SWEDEN: 300 UNITS WORLDWIDE
SPECIAL HYDROPHILIC ADSORBENTS (OPTIPOREฎ) FOR USE WITH
WATER VAPOR FOR FORMALDEHYDE ETC.
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Feed Stream
Clean Vent Stream
Condenser
Separator
Recovered
Liquid
PRESSURE SWING ADSORPTION PROCESS SCHEMATIC
(SORBATHENEฎ-DOW)
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ACTIVATED CARBON PSA SYSTEMS*
1. USED IN 90% OF ALL GASOLINE VAPOR RECOVERY SYSTEMS, 1,000
LOCATIONS IN USA, 500 NON-USA LOCATIONS FUEL LOADING
TERMINALS
2. 4 OUT OF 150 ACTIVATED CARBONS TESTED HAVE APPROPRIATE
RETENTIVITY ( 2 WOOD-BASED + 2 COAL-BASED) HIGH BUTANE
WORKING CAPACITY NEEDED ( > 0.065 glee)
3. US EPAREG. - 10 mg HC/liter
GERMAN REG. - 150mg HC/Nm3: 65 TIMES LOWER THAN US EPA REG.
4. DEMANDING VACUUM REQUIREMENT FOR REGENERATION
5. ADSORBS PRIMARILY THE NON-(CH4, C2H6) VOCs: C4H10, C5H12, C6H14, ETC.
Young and Tuttle in Topical Confernce Preprints (1997).
-------
AIR
4VENT
RECYCLE
PURGE
AIR
ADSORBERS
AIR/HYDROCARBON
VAPORS <
ป
-o
AIR/HYDROCARBON
VAPOR
ABSORBER
VACUUM
BOOSTER
BLOWER
c
SEPARATOR;
LIQUID
RING
VACUUM
PUMP
LIQUID HC
PROM
RETURN
PUMP
SEAL FLUID
PUMP
RECOVERED
i PRODUCT
TO
STORAGE
SUPPU
PUMP
SEAL FLUID
COOLER
ENHANCED EFFICIENCY VAPOR RECOVERY SYSTEM DESCRIPTION (John
Zink)
-------
ABSORPTION
1. HYDROPHILIC VOC: WATER IS ABSORBENT UNLESS AZEOTROPE IS
FORMED. CONVENTIONAL TOWERS MAY BE USED.
2. HYDROPHOBIC VOC: HEAVY HYDROCARBON ABSORBENTS. MEMBRANE-
BASED ABSORPTION AND STRIPPING BEING DEVELOPED.
-------
Air to Atmosphere
Water
Feed
Blower
Absorber
Surge
Tank
2
Prehealer
D
Acetone
(To Sales)
Distillation
Column
Cooler
Water Recycle
Absorption process for recovery of acetone from air
-------
From Poddar et al, AlChE J., 42, 3267 (1996)
VOC
enriched
air
Heater
_r
"VJE
Absorber
VOC lean air
Stripper
Cooler
Condenser
Vacuum
Pump
Solvent
Noncondensables
Schematic Process Diagram for VOC Removal by Membrane-based Absorption and
Stripping
-------
MEMBRANE PERMEATION
PERMEATES A VOC SELECTIVELY OVER N2/AIR VIA PRIMARILY A VOC-
SELECTIVE RUBBERY MEMBRANE OF PDMS (POLYDIMETHYLSILOXANE),
POMS (POLYOCTYLMETHYLSILOXANE)
1. SPIRAL-WOUND MODULES BY MTR, INC., PALO ALTO, CA: 40 UNITS OF
VAPORSEPฎ WORLDWIDE.
2. ROUND FLAT SHEET MEMBRANE IN A MEMBRANE ENVELOPE BY GKSS
(GEESTHACHT, GERMANY): 65 VAPOR RECOVERY PLANTS WORLDWIDE.
3. HOLLOW FIBER MEMBRANES HAVING PLASMA POLYMERIZED SILICONE
MEMBRANE BY AMT, INC., MINNETONKA, MN: SUCCESSFUL PILOT PLANT
TESTS.
-------
Compressor Condenser
Membrane
modules
VOC
in air
Liquid
VOC
Permeate
Basic flow diagram of a VOC recovery system based on the compression/condensation/
membrane hybrid configuration.
Nitrogen -
purge gas
Propylene-nitrogen
vent gas
(1)
Purge
bin
Polymer
product
Membrane
modules
Nitrogen stream,
96% nitrogen
6)
Hydrocarbon stream,
recycle to reactor
-------
Blower
Permeate
Recycle
Membrane
Module
voc ^
in Air
o
l
p
Purified
Air
Condenser
Vacuum
Pump
Liquid
VOC
VACUUM-DRIVEN VAPOR PERMEATION PROCESS
-------
Membrane
Feed
Channel
Purified Gas
Stream
(PRODUCT)
I
Vacuum on
SheU Side
VOC-Rich
Stream
(PERMEATE)
Stagnant
Contaminated Gas
VOC Laden
Stream
(FEED)
Product E
_ Closed
Vacuum on
SheU Side
VOC-Rich
Stream
(PERMEATE)
Feed End
Closed
At Time tads>t>0
At Time
cycle
Flow Swing Membrane Permeation (FSMP)
(from Obuskovic et al., I & EC Res., 37, 212 (1998))
-------
Air
Inlercooler Condenser
Feed
Compressor 1 Compressor 2
Phase
Separator
^ Acetone
(To Sales)
Condensation process for recovery of acetone from air.
-------
Condenser (1)
Condensate drain
Process Stream out
Economizer
-{XJ U*-ป
Exhaust
Liquid nitrogen supply
Condenser (2)
Condensate drain
Process Stream in
Kryoclean VOC control system
-------
TYPICAL PROCESS OPTIONS FOR REMOVAL OF VOCs
FROM VENT STREAMS**
L*
Membranes (nearly unlimited, 90-98%)
Pressure-swing adsorption (PSA) (probably about 20%, 99+%)
Temperature-swing adsorption: fixed bed (a few %, 99+%)
Moving/fluidized bed (a few %, 90-98%); Wheel-based (1000-5000 ppm, 90-98%)
Absorption (nearly unlimited, 90-98%)
Refrigeration/cooling (unlimited, 50-75%)
Freezing with, e.g., liquid nitrogen (unlimited 99+%)
* The first number in parenthesis is the maximum pollutant concentration
in mole percent in the feed; the second number is the maximum percent
removal.
** Keller and Humphrey, AlChE Annual Meeting, Preprints for Topical
Conference on Separation Science and Technology, p. 58, Los Angeles,
CA, November (1997).
-------
1
1
Process Selection Map
1
1
Dew Point
1 (40% Acetone)
I 4
| 2%
1 Acetone
(Concentration,
vol%
0.3%
1
1
|
Membrane Absorption Region I
| Region * 1 Membranes
i
to compete at low ; '
i acetone recovery *
Competing Region
Membrane, PSA, adsorption, and
absorption to compete in ttiis region.
_ _ _ . ^
PSA**
I
i Absorption
Region II
1.
Adsorption to
I compete at
' high acetone
recovery
100 1000 2000 10000
1
Air Feed Rate,
* PSA will be favored for clean air applications.
** Membranes will compete at rates up to 100*200 scfm.
i
i
i
i
scfm
-------
BASIC PRINCIPLES BEHIND VOC RECOVERY PROCESSES
AQUEOUS STREAMS
PHASE CHANGE PROCESSES; DISTILLATION
MASS SEPARATING AGENT-BASED PROCESSES
A. EQUILIBRIUM-BASED PROCESSES: ADSORPTION, STRIPPING,
MICELLAR SOLUBILIZATION
B. RATE-GOVERNED MEMBRANE PROCESSES: PERVAPORATION,
REVERSE OSMOSIS
FILTRATION PROCESSES; MEUF (MICELLAR ENHANCED
ULTRAFILTRATION)
MOST PROCESSES ARE HYBRID PROCESSES CONSISTING OF AT LEAST
TWO SEPARATION TECHNIQUES
-------
Open- and closed-loop systems
RH-modification unit
Wastewater inlet RH>80%
\
Chiller
VOC stream
RH<50%
Stripped
condensate
Counter-
current
air stripper
Water-
saturated
VOC condensate I
stream
Clean water out
Steam
tl
n y
Carbon
adsorbers
it
T
Steam
, Clean gas vented
j from system
Recycle loop for stripping air or nitrogen
Stripping agent
-------
STEAM-OR AIR-STRIPPING EFFECTIVENESS
FROM HWANG et al. (1992): IT
inf.dil
- 2 < Iog
10
log10K~>2
Highly Hydrophilic Low Mol. Wt.
DIFFICULT TO STRIP
EASIER TO STRIP
Ethylenediamine
Ethylene glycol
Formaldehyde
Acetic acid
Phenol
Methanol
Acetone
1-But a no I
Ethyl acetate
Methylene chloride
Chloroform
Benzene
Toluene
Carbon tetrachloride
Vinyl chloride
1-Hexane
-------
SURFACTANT-ENHANCED CARBON REGENERATION
WATER WITH
ORGANIC SOLUTE '
COLUMN
CLEANED
WATER
SURFACTANT
WITH
COLUMN
SURFACTANT
FLOOD
WATER WITH
COLUMN
WATER
FLOOD
WATER WITH
1C SOLUTE
COLUMN
CLEANED
WATER
f>
-------
LIQUID FEED SOLUTION
TREATED LIQUID FEED
SOLUTION
ORGANIC PHASE
VACUUM
PUMP
:- AQUEOUS PHASE
CONDENSER
PERVAPORATION (PV) PROCESS SCHEMATIC
-------
TYPICAL VOC/WATER SEPARATION FACTORS IN PERVAPORATION
VOC/Water Separation Factors for
Organophilic Pervaporation Membranes
Volatile Organic Compounds
1,000+
Benzene, Ethylbenzene, Toluene,
Xylenes, Trichloroethylene, Chloroform,
Vinyl Chloride, Ethylene Dichloride,
Methylene Chloride, Perfluorocarbons,
Hexane
100-1,000
Ethyl Acetate, Ethyl Butyrate, Hexanal,
Methyl Acetate, Methyl Ethyl Ketone
10-100
Propanols, Butanols, Acetone, Amyl
Alcohol, Acetaldehyde
1-10
Methanol, Ethanol, Phenol, Acetic Acid,
Ethylene Glycol, Dimethyl Formamide,
Dimethyl Acetamide
Athayde et al., Proc. 7th Pervaporation Conference, Reno, NV, p. 340 Feb. (1995)
-------
Surfactant Enhanced Soil Remediation with
Surfactant Recycle
Surfactant
Alcohol
Salt
-------
HYBRID PROCESSING FOR WASTEWATERS
AIR STRIPPING - ACTIVATED CARBON ADSORPTION FROM STRIPPING AIR
STEAM STRIPPING CONDENSED ORGANICS
WASTEWATER - REVERSE OSMOSIS -
CONCENTRATE RECOVER BY PERVAP
ACTIVATED CARBON ADSORPTION - STEAM STRIPPING
SOLVENT EXTRACTION - DISTILLATION
-------
VOC-CONTAMINATED WASTEWATER
TREATMENT OPTIONS*
a
cd
60
*\
ฃ
D
1000
100
10
0.1
Chemical
- oxidation,
UV
destruction,
"or air stripping/
carbon
adsorption
Steam stripping
-^^
^^~^^^^^^
^^^
Pervaporation
Distillation/
Incineration
Offsite disposal
0.001
0.01 0.1 1 10
VOC concentration (%)
100
Note: gal/min *3.7848 = L/min
* Cox and Baker, Industrial Wastewater, p36, Jan/Feb(1998)
-------
CONCLUDING REMARKS
1. NEED COMPARATIVE ECONOMICS AND EVALUATION FOR AIR/N2 STREAMS
HAVING a) LARGE FLOW RATES b) HYDROPHOBIC VOCs AND c) HYDROPHOBIC
AND HYDROPHILIC VOCs
2. NEED COMPARATIVE ECONOMICS AND EVALUATION FOR AQUEOUS WASTE
STREAMS VIS-A-VIS DIFFERENT PROCESSES (e.g., STRIPPING, RO, PERVAP,
SOLVENT EXTRACTION, DISTILLATION) AND COMBINATIONS OF PROCESSES
3. NEED COMPACT AND FLEXIBLE DEVICES FOR VENTS FROM SMALL-SCALE
EQUIPMENT
4. FOR POLAR VOCs, NEED MUCH MORE VOC-SELECTIVE PERVAP MEMBRANES
5. NEED MEMBRANE-BASED COMPACT AND CHEAPER STEAM STRIPPERS
6. NEED SELECTIVE AND STABLE ADSORBENTS STRIPPABLE VIA SMALL AT
CHANGES
7. ARE THE CURRENT PRESSURE SWING PROCESSES THE BEST THAT WE CAN
HAVE?
-------
I
I
I
I
I
I
-------
-------
-------
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^::4to& v. .<&,i^^^
a^ili^^
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>'.^sฉ^:^^>lฅt^^
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ซ H('-i'.' "'ฃ-'vV'$T;''v^<;^' >, V*'^'*;1^ ',.,wKS-ivv, -'--iPM,..ii.^M"ek"'lK5iiv>'^X(ป-'fP4", "* V.-v:'.ซ,.-. ;.^V',t''.'...";>'.i.'-"'.:;. . jp, i-'V'--^'-'':^ "i*.',:-'.1iv^i-^;1'''v-'ft-i,1'.'..-.:-!?;-^^'"'*'- ^i'^.'-ft^ A^:;i'^,;.,-'.ซ?">wfa;*&-? !?-,,'^:?;"'r 'V.'s
.^:j7^i'."^-""-^^%.Jv-; ,.';-^:':-\:v-^Jao^y;. v .*KS; -^:;; ^;:' "".:E ;> v- ':kฐ0;iป?S *ซ ^'q^'^v^-'^'1-'1,.';;1': :^:M;^M.''V;/ .l--.i.i.ir'..;!;" r^^xv^*;;^;^ r1'-^ i-.'i'?';1:;.,/-,;" -;Vf^;/ ''''^";^-j'./i'^i^v-^',''ftSj*M
iltefli*^^
^iiM^lฅMf:v'^ซ::f^
-------
-------
VOC Recovery Research Programs
Industrial Research
What is Innovative Technology?
New Application of Existing Technology
New Development of Existing Technology
Totally New Concept
-------
New Application of Existing Technology
Membrane Separation Technology
> Recovery of VOCs via permeable membranes
> Application to compounds that are not recovered well via adsorption
and condensation
+ Application to halogenated solvents is growing
> Good for recovery of expensive solvents
Biofiltration
* Destruction of VOCs via biologically active filter bed
> 50% success rate for sustained operation
> Some success with gasoline and BTX vapor streams
> Low operating costs and energy requirements
Photochemical Destruction Technologies
> Destruction of VOCs via UV radiation and oxidants
> Limited commercial applications
-------
New Development of Existing Technology
New adsorbents
> Alternatives to granular activated carbon
> Zeolites
> Polymers
> Carbon fibers
* Improved performance for high boiling point compounds, humid vapor
streams, exothermic adsorption reactions
New bed regeneration options
> Refrigeration
> Solvents (e.g., acetone, methanol)
> Vacuum
* Inert gas (e.g., nitrogen)
> Resistive electrical heating
> Microwave heating
New packing materials to reduce fouling
Cryogenic fluids for condensation (liquid nitrogen, liquid carbon dioxide)
-------
Totally New Concept
Destruction of VOCs via ionized gas (plasma)
Corona Discharge Plasma Reactors
Electron Beam Plasma Reactors
-------
Market Drivers for Innovative Technologies
Type/concentration of VOCs in exhaust stream
Exhaust stream flow rate
Regulatory duress
-------
Innovative Technologies: Benefits
Permit Waivers
Demonstration Cofunding
-------
Innovative Technologies: Risks
Unknown operating/maintenance costs
Scale-up problems
Unacceptable process changes
Unknown waste generation costs
Unknown long-term operational reliability
Unknown long-term reliability to meet regulatory performance standards
-------
-------
VOC Recovery Research at
EPA-ORD
Teresa Marten
Clean Processes and Products Branch
VOC Recovery Seminar
Cincinnati, OH
September 16-17, 1998
-------
Risk Paradigm
Risk Management/
Risk Assessment
Paradigm
Statutory and Legal
Considerations
Dose-Response
Assessment
Public Health
Considerations
Social Factors
Hazard
Identification
Risk
Characterization
Economic
Factors
Political
Considerations
Risk
PAMfl^^^BB
Management
Options
Exposure
Assessment
Risk Assessment
Risk Management
-------
Technology Research
Pervaporation
Temperature Swing Sorption
Pollution Prevention Tools
-------
Pervaporation:
Permeation & Evaporation
Liquid
Vapor
Water
VOC
VOC-Selective Membrane
(Non-porous)
-------
Pervaporation Process Units
Flowmeter
Liquid Feed
Feed Pump
Filter
Vent
Vacuum
Pump
Permeate
Vapor
Condensers
Chiller
Unit 1 1
I
Permeate
Condensate
Reservoirs
Membrane
Module
Residual
Liquid
-------
Projects
Industrial P2 Pervaporation Research
Remediation Fluid Recycling
*
Pervaporation Performance Prediction
Software & Database (PPPS&D)
Polymer/Ceramic Composite Membranes
Conductive Membranes and Films for
Separation Processes
-------
Functions of Pervaporation
Software Program
Version 1
- Educate
- Research Database
- Predict Bench-scale Performance
Version 2
- Predict Pilot-scale Performance
Version 3
- Pilot Unit Cost Element
-------
Temperature Swing Sorption
Uses a polymeric sorbent material.
Sorbent is cooled during sorption phase to
increase capacity.
Regeneration is completed in place.
The presence of water vapor should not
affect capacity.
-------
TSS Bench Unit
BmchUntt
Computer Ior temp.
Temperature
oontrotled
ohember
-------
Technical Objective
To develop a cost-effective technology
suitable for the recovery of VOC emissions
from paint spray booth exhaust.
Recovery becomes viable if low VOC
coating formulations are not appropriate, or
reductions are mandated by a SIP.
-------
Pollution Prevention Analytical
Tools Development
Process Simulation Software
(Waste Reduction Algorithm)
Life Cycle Tools: Inventory and Impact
Assessment
-------
-------
Ji^K.:ซ!rsi'-flfflKป
^w?^w^!wSSS
MlSMiซKiปซ
iffi^^JSW^
-------
-------
New Paradigm for Lower
Cost Adsorption
Processing SHERPA
Presented at
Volatile Organic Compounds (VOC)
Recovery Seminar
September 16-17, 1998
Cincinnati, Ohio
William J. Asher
Principal Chemical Engineer
Chemical Engineering Development Center
SRI International
-------
Flow Path Reduced
From: Several Feet
To: A Fraction of an Inch
All advantages come from the shorter flow path
-------
SHERPA
Can Use Pressure Swing Adsorption (PSA)
Smaller by a factor of 100
Lower cost
* More widely applicable
-------
Pressure Swing Adsorption Cycle
1. Pressurization
Increase pressure from
low to high of cycle
Flow in Feed
Flow out....None
2. High Pressure Flow
Flow through at
high pressure
Flow in Feed
Flow out....Adsorbate
depleted gas
Return to Step 1
3. Depressurization
Adsorbate removal
from adsorbent. Decrease
pressure from high to low
Flo win Feed
Flow out....Adsorbate
for Recovery
-------
PSA Bed Configurations
Treated Gas
Hollow
Fibers
Adsorbent
Particles
ซ I Ml I I
Feed Gas -
Conventional Contactor
Hollow Fiber Contactor
-------
Engineering Analysis
Pass Throuah Hollow Fiber Mechanisms of T
\~'
^:!
V:=:
(=:=:
(:=:!
t"*
}.-
(::*
V:j:
|te=
>:-:
P
t
A
t
4
T
t
:-r- -:
:::: ::
*-ป-*-ป
I- 1 I *
*ป*"-ป
t
t
1
t
t
:: ::
-_-
:- :-
*-ป
t
1
1
t
t
-ป*ป
:>:=::
:=:=:=:
-:'-:
m m m
-::-:
ปซซ>
t
t
1
t
t
* Distribution Headers Flow
^ Flow Through Hollow Fibers Flow
*: 1 Transport Through Hollow Fiber Walls Diffusion
;;. ) Transport from Hollow Fibers to Diffusion
H ( External Surface of Adsorbent Particles
> j Transport Inside the Adsorbent Particles Diffusion
:=i
=:{
II (
:| [
j;l
*"" r
*- f
Limitation
-------
Different Flow Path Creates Very
Large Advantage
t
t
t
I
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
Initial configuration
New configuration
-------
Much Shorter Flow Path Produces Major
Advantages
State of the Art
t
O)
-------
Invented Configuration Eliminates
Limitation
Mechanism of Transport
Pass Through
Hollow Fiber
SRI Contactor
Distribution Headers
Flow Through Hollow Fibers
Transport through Hollow
Fiber Walls
Transport from Hollow Fibers
to External Surface of Adsorbent Particles
Transport Inside the Adsorbent
Particles
Flow
Flow
Diffusion
Diffusion
Flow
Flow
Flow
Diffusion Flow
(Limitation Eliminated)
Diffusion
-------
New Flow Path Invention
* Eliminates limiting step of diffusion to adsorbent
particles
* Allows cycle time to be reduced by a factor of up to 100
Bed size directly proportional to cycle time
Bed size can be reduced by a factor of up to 100
* U.S. Patent 5,693,230 Issued Dec. 2,1997
-------
New Paradigm
Different in kind and concept
All previous hollow fiber adsorbers
All previous rapid cycle PSA's
-------
Removal of Butane From Methane Using
New SRI Contactor
CD
0)
0)
e
CD
C
.o
"5
"c
CD
O
C
o
O
o
o
Required
90%
Retention
Experimental
Removal
Adequate
Practical Removal
100
0
Theoretical Ideal Removal
Perfect flow distribution
Infinite rates
I Theoretical Max.
"r 90% Retention
Experimental
J, 90% Retention
100 200 300
Feed Processed (m moles/g carbon)
Feed was 2 mole
%C4HioinCH4
Adsorbent was
activated carbon
400
500
-------
Feasibility of New Contactor Has Been
Experimentally Established
-------
Contactor Fabrication
iLซi*j^^
Solid Filaments
Porous Hollow Elements
Product
\
Sealed Ends
inlet
Seal
Seal
-------
Spiral Configuration of Contactor
Woven elements
with sorbent and
impermeable layer
Porous Hollow Elements
Solid Filament
Impermeable Layer
Spiral wound hollow
fiber contactor Solid Core
Shell Exterior
Solid Filament
Porous Hollow Elements
-Sorbent
Impermeable Layer
Material to Seal Between
Spiral and Shell
-------
Manufacturing Process for SPD
Transverse Flow Contactors
Celgardฎ Fiber
Fabric
Center Tube with Central Plug
Celgard Fiber
3 Resin Lines Orientation
From Hoechst Celanese (5/25/94)
-------
Applications
voc
Natural Gas
Petrochemical
Light Ends
Other Gases
Removal and
Recovery of:
Removal and/or
Recovery of:
Separations
Removal and/or
Recovery of:
Using Established
Absorbents
Using New
Absorbents
Natural Gas Liquids
Water
Acid Gases
Propylene from
propane
O,
N'
H2O
CO2
Ho
Any equilibrium adsorption
separation that small
contactors make economical
Differential rate absorption
separations, including
those requiring cycle times
under one second
-------
Moving Toward Commercial Applications
SRI in discussion with
Hollow fiber producer and module fabricator
Valve manufacture for < 1 sec valves
-------
Application Opportunity
Thousands of separation in the literature
New sorbent systems being developed
* Much smaller, low cost units
* Important opportunities to address now?
-------
For More Information, Contact
William J. Asher
Principal Chemical Engineer
Chemical Engineering Development Center
SRI International
(650) 859-2823 Phone
(650) 859-3678 Fax
-------
SOLVENT RECOVERY
APPLICATIONS AT 3M
OVERVIEW
AND
CASE STUDY
James J. Carmaker
9/16/98
-------
3M VOC CONTROL SYSTEMS
110 VOC AIR POLLUTION CONTROL
SYSTEMS WORLD WIDE
- 85 THERMAL OXIDIZERS
- 25 SOLVENT RECOVERY UNITS
FIRST SYSTEMS INSTALLED IN 1970's
1987 - CORPORATE AIR EMISSION
REDUCTION PROGRAM
TOTAL INVESTMENT: $260 MILLION
-------
AIR EMISSION REDUCTION
PROGRAM (AERP)
GLOBAL CORPORATE POLICY -1987
ALL SOURCES WHICH EMIT MORE
THAN 100 TONS/YEAR MUST MEET:
- LOCAL GOVERNMENT EMISSION
STANDARDS AND
- AERP REQUIREMENTS
EXISTING SOURCES: 81% CONTROL
NEW SOURCES: 90% CONTROL
-------
AERP RESULTS
0.
o
o
o
-------
ENVIRONMENTAL AWARDS
1996 - PRESIDENT'S SUSTAINABLE
DEVELOPMENT AWARD FOR 3P PROGRAM
1995 - ENVIRONMENTAL CHAMPIONS AWARD
FOR AIR EMISSION REDUCTIONS (U.S. EPA)
' 1995 - ENERGY EFFICIENCY AWARD FOR
BRAYTON CYCLE SOLVENT RECOVERY SYSTEM
(ALLIANCE TO SAVE ENERGY)
1991 - STRATOSPHERIC OZONE PROTECTION
AWARD (U.S. EPA)
1991 - WINNER OF PRESIDENT'S ENVIRONMENT &
CONSERVATION CHALLENGE AWARD CITATION
-------
SOLVENT RECOVERY
SYSTEMS
CARBON ADSORPTION - 15
- STEAM REGENERATION (13)
- INERT GAS REGENERATION (2)
INERT GAS CONDENSATION - 10
LIQUID WET SCRAP DISTILLATION - 5
-------
SOLVENT RECOVERY
SYSTEMS - AIR STREAMS
CARBON ADSORPTION
- AIRFLOW: 6,000 - 102,000 SCFM
INERT GAS CONDENSATION
-SOL VENT RATES: 5-900LBS/HR
SOLVENTS
- HEXANE, HEPTANE, TOLUENE, NAPTHA, ETHANOL,
ISOPROPYL ALCOHOL, ETHYL ACETATE, METHYL
ETHYL KETONE, CYCLOHEXANONE,
CARBON BISULFIDE
-------
SOLVENT RECOVERY
APPLICATIONS
HIGH VOC USAGE RATES
FIXED SOLVENT BLEND
RE-USE SOLVENT IN PROCESS
HIGH SOLVENT VALUE
CONTINUOUS OPERATION
-------
3M HUTCHINSON, MN
SOLVENT RECOVERY CASE STUDY
MAGNETIC AUDIO/VIDEO TAPE MANUFACTURING
MEK, TOLUENE, CYCLOHEXANONE
SOLVENT RECOVERY PLANT INSTALLED IN 1990
- CARBON ADSORPTION
- STEAM REGENERATION
- SOLVENT DISTILLATION
CONTINUOUS PROCESS WITH TWO OPERATORS
24 HOURS/DAY, 360 DAYS PER YEAR
-------
SOLVENT RECOVERY PLANT
DESIGN PARAMETERS
AIR FLOW: 102,000 SCFM
SOLVENT RATE: 5,100 LBS/HR
- METHYL ETHYL KETONE (55%)
- TOLUENE (30%)
- CYCLOHEXANONE (15%)
97% RECOVERY EFFICIENCY
99% PURITY
-------
SRU PROCESS FLOW DIAGRAM
EXHAUST
AIR
A
CARBON
'ADSORBERS
A
DISTILLATION
MEK
TOLUENE
CYCLOHEXANDNE
VASTEWATER
SCRAP SOLVENT
DESDRBATE
-------
ADSORPTION PROCESS FLOW DIAGRAM
INLET SLA
a
aa
uu
SLA STEAM
HUMIDIFIERS
STEAM
CODLING
BLDWERS
SURGE
BOTTLE
1
QL
ADSORBER
ADSORBER
ADSORBER
.DESORBATE
J_
STEAM
PRIMARY
CONDENSER
TD
SURGE
JLBOTTLE
1
-O-
ADSORBER
ADSDRBER
ADSORBER
.DESDRBATE
j i i PRIMARY
DISTILLATION CONDENSER
-------
ADSORBER SCHEMATIC
CJ
T
QUENCH
CO
^^
S N
HC
1C
X
TDP
DRAIN
PCDNSERVATIDN
ฉ VENT
37,600 LBS DF CARBDK 40" BED DEPTH
STEAM
-ฉ
NITROGEN
CODLING AIR
QUENCH
DESDRBATE TD
CONDENSERS
LJ
BOTTOM
DRAIN
CD
^-^
^-^
HC
*>
-------
ADSORBER CYCLES
ADSORPTION - 132 MINUTES
- 75,000 SCFM OF SLA
REGENERATION - 40 MINUTES
- 16,500 LBS/HR OF STEAM
COOLING - 23 MINUTES
- 14,000 SCFM OF AMBIENT AIR
STANDBY - 1 MINUTE
(4 IN ADSORB, 1 IN REGENERATION, 1 IN COOLING)
-------
ADSORPTION PLANT PERFORMANCE
75,000 SCFM OF SLA, 95 DEG F, 45% R.H.
2,800 LBS/HR OF SOLVENT
99.5% ADSORPTION EFFICIENCY
4 - 10% CARBON WORKING CAPACITY
5 - 8 LBS STEAM / LB OF RECOVERED SOLVENT
REACTIVE CHEMISTRY
- DIACETYL AND ADIPIC ACID FORMATION
- KETONE FIRE POTENTIAL (CO < 5 PPM)
-------
DISTILLATION PROCESS
67,000 LBS/DAY OF SOLVENT
WATER / SOLVENT SEPARATION
- DECANTERS AND WASTEWATER
STRIPPING COLUMN
SOLVENT NEUTRALIZATION
- WASH COLUMN
SOLVENT DISTILLATION
- DEHYDRATION, MEK, TOLUENE,
CYCLOHEXANONE COLUMNS
-------
DISTILLATION PROCESS FLOW DIAGRAM
FRDM SURGE BOTTLE
RECYCLED SOLVENT
PRIMARY
DECANTER
W V
WATER
LAYER
TANK
A
162 F
SECONDARY
DECANTER
WASTE
WATER
STRIPPER
216 F
A
SOLVENT
LAYER
TANK
WASH
COLUMN
V
SEWER
.HSSD4
DEHYDRATION
DECANTER
CYCLD-
HEXANDNE
COLUMN
(VACUUM)
HI BDILERS
-------
RECOVERED SOLVENT
MAY, 1998
MEK
TOLUENE
CYCLOHEXANONE
TOTALS
MEK
TOLUENE
CYCLOHEXANONE
APPLIED. LBS
892,497
483,246
244,691
1,621,441
RECOVERED, LBS
907,430
482,928
220,393
% OF TOTAL
55.1
29.8
15.1
100.0
% NET APPLIED
101.7
99.9
90.1
TOTALS
1,610,751
99.4
-------
RECOVERED SOLVENT
SPECIFICATIONS
CYCLO-
PARAMETER MEK TOLUENE HEXANONE
GC PURITY >99.00 >99.00 >98.50
SPECIFIC GRAVITY 0.795-0.805 0.864-0.874 0.935-0.946
REFRACTIVE INDEX 1.3755-1.3785 1.4915-1.4978 1.4460-1.4500
WATER, % 0.10 0.05 0.10
DIACETYL, ppm <40 <30 <30
ACIDITY, % <0.003 <0.003 <0.02
(as acetic) (as acetic) (as adipic)
INFRARED Pass Pass Pass
-------
OPERATIONAL HISTORY
1990 START-UP
1991 ADSORBER CARBON BED FIRE
AND ADSORBER IMPLOSION
1993 PROCESS REFORMULATION AND
CHLORIDE REDUCTION
1996 DISCONTINUED MANUFACTURE
OF 3M VHS CASSETTES
1997 MACT MODIFICATIONS
-------
MACT MODIFICATIONS
(MAXIMUM ACHIEVABLE CONTROL TECHNOLOGY)
MIXING KETTLE VENTS (41)
WASH TANK VENTS (3)
SOLVENT RECOVERY VENTS
-TANKS/VESSELS (15)
- DISTILLATION COLUMNS (5)
-------
MIXING KETTLE - VENT CONTROLS
AIR
INTAKE
FA O
FA
CD
TYPICAL
MIXING
KETTLE
ซ25X LFL)
FA
do
TYPICAL
MIXING
KETTLE
TO SLA
DUCT/SRU
FAN
BALANCING
DAMPERS
u
Q
ID
-------
WASH TANKS - VENT CONTROLS
A
BALANCING
DAMPERS
A
A
TYPICAL
WASH TANK
ซ25X LFD
FAN
TYPICAL
WASH TANK
TD ATM
STACK _L
DAMPER [MO
TD SLA
DUCT/SRU
SOURCE
DAMPER
-------
SOLVENT RECOVERY - VENT CONTROLS
o4 CV
>? FA
o
NITROGEN
GAS
'PAD' VALVE
'DEPAD' VALVE
TD SRU
PT ) 0.5 TD 1.0' W.C.
TYPICAL SRU TANK
DR PROCESS VESSEL
TD SRU
-------
CAPITAL & OPERATING COSTS
> CAPITAL
- 1990 INSTALLATION: $19,500,000
- RE-COMMISSIONING: $2,500,000
- MACT MODIFICATIONS: $1,400,000
- TOTAL: $23,400,000
ANNUAL OPERATING $3,300,000
-------
RECOVERED SOLVENT VALUE
SOLVENT
VALUE
$/LB
SOLVENT
RECOVERED
LBS/YR
SOLVEN
VALU
$/Y
MEK
0.38
13,200,000
5,016,00
TOLUENE
0.16
7,200,000
1,152,00
CYCLO-
HEXANONE
0.50
3,600,000
1,800,00
TOTALS
24,000,000
$7,968,00
-------
-------
-------
The Economics of
VOC Recovery
Using the OAQPS
Cost Manual
as a Tool for
Choosing the Right
Reduction Strategy
-------
The OAQPS Cost Manual
Fundamental Concepts
Cost Categories
Choosing a Strategy to Reduce VOCs
The Economics of Regulation
Office of Air and Radiaton
Offcfl.of
Air OualSy
Planning and Standards
^ Standards
Information
Tnsft<'
Policy 4
AifChii%
StrateQieii
Stsntfanis actio
_ OKHW Jnnovatwa Huim Rซks ,
Pe^cy* Stratagte^f Bfecwi pxposure
StซtteBซ* econwries standards AtMssment
<3roop
Cofltral
Cost Team
Bill VaiavtiK, Senior Cost Expert
Daniel MutMttl, Swlor Economist
ErrjWlons,
Analysis
Oivblwi
-------
Bill Vatavuk
919-541-5309
vatavuk.bill@epa.gov
Daniel Mussatti
919-541-0032
mussatti.dan@epa.gov
Fax: 919-541-0839
US EPA/OAQPS/ISEG
MD-15
RTP,NC 27711
The OAQPS Cost Manual
http://www.epa.gov/
I ttn/catc/products.
html#cccinfo
ILJI ILJI IULJ
-------
The Cost Manual (cont.)
"Uniqueness" of the Manual
- Key reference for other cost manuals
- General, rather than control-specific
- More rigorous and complete
- Designed for estimating costs for
regulatory development (RIA, ICR, etc.)
The Cost Manual (cont)
Eleven Chapters
- Intro
- General Discussion of Costs
- 8 Chapters on specific Control Devices
(Incinerators, Flares, Adsorbers, Filters,
Precipitators, Condensers, Hoods, Ducts,
and Stacks)
- NOx Control Devices (forthcoming)
- Permanent Total Enclosures
(forthcoming)
-------
Fundamental Concepts
The Types of Costs
Accounting Costs
Social Costs
= Economic Costs
Fundamental Concepts
Accounting Costs
Accounting Costs
Annual Cost
Direct & Indirect
Fixed & Variable
Recovery and Salvage
Cost of Investment
Land & Capital
Salvage Value
-------
Fundamental Concepts:
Social Costs
Tangible
- Increased Morbidity / Mortality
- Property Damage
Soiling & Staining
Corrosion
- Productive Loss
- Crop and Livestock Damage
Intangible
- Habitat Loss
- Diminished Biodiversity
- Aesthetic Loss
- Option Values
- Existence Values
Definitions
Control is the management of the pollutant stream.
Control is not the same as Destruction.
Strategy: an alternative method for reducing VOC
emissions
Recovery: the process of harvesting VOCs from the
pollutant stream
Recycling / re-use: the process of exploiting the
economic value of the recovered portion of the
pollutant stream
-------
The Firm's Short Term
Decision Process
Maximize profits / revenues
Minimize costs
The Firm's Decision Process
Choose the control strategy that has
the lowest marginal cost of operation
over the relevant range, (short term)
Choose the control strategy with:
- the highest Net Present Value, (long term)
-------
The Anatomy of Costs
$
Marginal Cost
Average Cost
Q
The Anatomy of Costs
Marginal
Cost
Strategy 1Strategy 2
Qi
Q2 Q
-------
The Anatomy of Costs
Marginal
Cost
Strategy 1
Strategy 2
Ql
Q2 Q
The Anatomy of Costs
Marginal
Cost
Strategy 1
Strategy 2*i
Strategy 2
Ql Q3 Q2 Q
-------
CASE STUDY - Background
Graphics printing enterprise
4 different solvents used
Single Site Recovery
- Re-capture not an option
- Disposal involved potential
RCRA liability
- Incineration
CASE STUDY - Action
Strategy: Reformulation
The source went to single solvent (Hexane)
for all processes
Installed Carbon Adsorbers at single
collection site to recover solvent from
outflow
-------
CASE STUDY - Results
Single solvent captured at a single site
let the printer become a net supplier
ofHEXANE.
Met standards at
reduced compliance
cost.
Choosing a Reduction Strategy
Step One
START AT THE END
- Identify the compounds in the effluent
stream to be controlled.
- Does the effluent stream have value?
- Does the effluent stream contain toxic
substances?
Are those toxic substances valuable?
How so you dispose of those toxic
substances?
-------
Choosing a Reduction Strategy
Step Two
IF THE EFFLUENT STREAM
CONTAINS TOXIC SUBSTANCES
THAT HAVE NO VALUE
- Incineration
is probably the
cost effective
alternative
Choosing a Reduction Strategy
Step Three
IF THE EFFLUENT STREAM
CONTAINS SUBSTANCES THAT
HAVE SALVAGE VALUE
Compare the cost of
incineration to the
cost (net of salvage
value) of alternative
recapture technologies
-------
The Anatomy of Costs
Marginal
Cost
Strategy 1
Strategy 2
Strategy 2
Ql Q3 Q2 Q
HOW MUCH CONTROL DO
YOU NEED?
-------
NSR/PSD
MACT
BAD NEWS / GOOD NEWS
BAD NEWS
The cost of reduction
is directly related to
the level of reduction,
and the level of reduction
is highly correlated to
how many regulations
apply to the industry.
-------
GOOD NEWS
C ompliance
Advisor
Welcome to the
Compliance Advisor Development Group
World Wide Web Site
http://www.epa.gov/ttn/catc/
The Air Compliance Advisor
(AC A)
An integrated package of databases, algorithms and
models, that can solve complex air management
problems
A framework in which many models operate (many
more can be added)
A customizable decision support tool for end-users
to play "what-if" scenario analyses with their data
-------
DoD' EPA i
Strategic Environmental Research
and Development Program
Improving Mission Readiness through
Environmental Research
The ACA Components
Data and analysis algorithms
Data libraries
Chemical properties
Regulatory data
Hierarchy of source types
Emission control technologies
Pollution Prevention (P2)
"Suggestions" data
-------
Control Technologies
Considered
carbon adsorbers (single bed & multiple
bed)
thermal incinerators (catalytic,
recuperative, regenerative)
flares (self-supported, guy-supported, and
derrick-supported)
gas absorbers
refrigerated condensers
wet scrubbers for PM (venturi, impact)
baghouses (pulse-jet, reverse air, shaker)
Uses Algorithms From:
AP-42
WaterS documentation
AQUIS
Calculates actual and potential emission rates
Means of documenting emission factor ratings and
references (75% complete) I
-------
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EPA VOC Recovery Seminar
September 16-17
Cincinnati, Ohio
That's Our Business
-------
Technologies
Rotary Concentrator
Carbon Fiber Adsorption
That's Our Business
Era
-------
Rotary Concentrator
Functioning
Continuous
- Adsorption
- Desorption (hot air)
- Cooling
Adsorbent impregnated
honeycomb element in
continuous motion
Adsorbent
- Carbon
- Zeolite
- Combination
That's Our Business
-------
VOC Concentrator /
Oxidation System
Exhaust
90-95% Clean
of Process Exhaust
Process
Exhaust
Filter House (x3)
Secondary Heat
Recovery System
Thermal Oxidation -
Recuperative, Regenerative, Catalytic
That's Our Business
-------
Rotary Concentrator
Participate Removal
r
1
1
Venturi Scrubber ^
Dry Filter [-
WEP Y
That's Our Business
Concentration
Rotary
Concentrator
Final Treatment
RTO
HTO
I Recuperative Oxidizer |
KAR Catalytic Oxidizer |
TTX Catalytic Oxidizer I
I Recovery Adsorber j
| Direct Condensation |
-------
Rotary Concentrator
Clean Process Air
Hot
Desorption Air
Solvent-Laden
Process Air
Optional Smoothing
Rotor Drive
Adsorbent Me
Solvent-Laden
Desorption Air
That's Our Business
Mi
-------
Air Flow
Schematic
Clean
Oxidizer
Exhaust
Clean
Process
Air
Process
Fan
OXIDIZER
CONCENTRATOR
Solvent-Laden
Process Air
That's Our Business
jj
-------
The Diirr DISC
Disk Integrated Solvent Concentrator System
Clean
Process
Air
Thermal Oxidizer with
Heat Recovery
Concentrator
Disk
Clean
Process
Air
Solvent Laden
Process Air
That's Our Business
-------
Rotary Concentrator
Application
High volume low concentration streams
- Industries
Paint Spray Booths (automotive and others)
Printing
Semiconductor
Fiber Glass Plastic (styrene) Manufacturing
- Volume treated
5,000 to 600,000 SCFM
Single Unit up to 50,000 SCFM
That's Our Business
-------
Rotary Concentrator
Application
High volume low concentration streams
- vocs
Alcohols
Aliphatics
Ketones
Glycols
Chlorinated
That's Our Business
-------
Temperature
Rotary Concentrator
Application
Concentration of VOCs
Humidity
Removal Efficiency
1000 PPMV
<100ฐF
(solvent Dependent)
< 65% Carbon
<95% Zeolite
> 95%
That's Our Business
QM3
-------
WIXOM BASECOAT ROTARY CARBON UNIT 2-2
PERFORMANCE TEST 11-3-93
60 120 180 240 300 360 420 480 540 600 660 720 780 840 900 960 1020 1080 1140 1200
TIME (SECONDS)
GAG AVG
143 PPM
OUTLET AVG
3.73 PPM
DESORB AVG
1561 PPM
REMOVAL
EFFICIENCY
97.5%
CONCENTRATION
RATI010.3:1
That's Our Business
E
-------
Rotary Concentrator for
Solvent Recovery
Pre-concentrator for a conventional solvent
recovery system
Solvent recovery for VOCs with High LELs
e.g. TCE (80,000 ppmv)
Concentrators in series to achieve 100
times concentration (patented design)
- Continuous solvent recovery
- Low pressure drop
- Compact
- Lightweight
That's Our Business
-------
KF - Carbon Fiber for Solvent
Recovery
Batch
- Adsorption
- Oesorption (steam)
- Cooling
High capacity carbon fiber non-woven mats
in baghouse type configuration
That's Our Business
-------
^y 'f*.
ff. *"
3 ?
sฃ J.'
? K :ฃ
fl^1' \
KM - \
t ~ v,
ifr^v
9\,% ! - 4
-'' J\'' f y^-/
> ฃ" * f tata
"/ 'ftx <
< * V\
> - ฅซ
*-,. viv
' , ^ C*'
1 f -'J'\- - t
wvwfffs+fWF B >
7 J > '
-------
KF -Application
High concentration (> 1000 ppmv) streams
- Industries
Chemical Manufacturing
Pharmaceutical
Painting and Coating Industry
Printing
- Volumes treated
1000 SCFM onwards
single unit up to 15,000 SCFM
That's Our Business
-------
KF -Application
High concentration (> 1000 ppmv) streams
- vocs
* Alcohols: Excluding Methanol & Ethanol
Alphatics
Aromatics
Ketones
Glycols
Chlorinated
That's Our Business
M3
-------
Temperature
KF - Application
Concentration of VOCs > 1000 ppmv
Humidity
Removal Efficiency
<150ฐF
(solvent dependent)
< 95%
90-98%
That's Our Business
DM3
-------
KF vs Packed Bed
Parameter
Efficiency
Pressure Drop
Steam Consumption
Weight
Foot Print
Quality of Recovered
Solvent
KF
Lower
Lower
Small
High
Packed Bad
Similar
Similar
Higher
Higher
Large
Moderate
That's Our Business
-------
Comparison of Pore Structure
of Granular Activated Carbon
and Activated Carbon Fiber
Fiber Surface \
micropore
v.
Granulated
._,
Macro-/ \
That's Our Business
-------
COMPARISONS BETWEEN ACF AND g-AC
IN ADSORPTION AND DESORPTION OF TETRACHLOROETHYLENE
ADSORPTION (ADS); 15,000 ppm, 16cm/s
DESOHPTION tDES); 85ฐC N2 Gas, 16 cm/s
THICKNESS OF ADSORBENTS: 2 cm
DBS 2&-*-ADS 3 --
That's Our Business
-------
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M & W Industries, Inc.
CONDENSORB VOC
RE CO VER YSYS TEM
-------
Lowest Operatin
Adsorbe
ite
Celts
e95-10T/oof
s me,
s and
\ i ^
id other^ater soluble
(O
Acet
fronlproces)s exhaus
Regerieration of cellk releases high
concejiWtions of contaminants, in an u
low flew of warm air.
-------
denser
Air Regen
team Used for Keg
No
Steam Boile
No Decanting or pH
hustment Nece
-------
Lowest Overall
S]raem consunn
&
x
and nofuel.
Rec^very^oi VOC dr HAP allows s
achieve a return on investment.
-------
w ^fc
Condensorb Adsorption / Recovery
System
Process
Exhaust
. Exhaust
>95% Clean
Concentrator
M & W Industries, Inc.
Regeneration
Air
To Concentrator for
Final Treatment
Condenser
Recovered
VOC/HAP
-------
Advantages
4-
4-
Recovered VOC/HAP adds
economic benefit
No Fuel Consumption
No NOx Production
Very Low Pressure Drop-
Relatively Quiet
95% Minimum Recovery
Adsorption Media Easily
Replaced / Updated
Very High Uptime Reliability
Existing Solvent Recovery
system can be retrofitted
VOC Control -
tern
4 Paniculate Filtration may be
needed
4- Inlet Temperature Limited to
140ฐF
M & W Industries, Inc.
-------
Economic Payback of the
graphic Prin
ent Operati
Rec
inclu1
recov
per g
solvent
st of $3
\s
gallon rqc
^w' VO N
neutralize
Losing jdt least 50 gallons of Ethanol per
day using traditional recovery technology
-------
graphic Prin
Condensor
costs
st redu
covere
o steam c
^l~^^^-j-\J>\^~j-s
o neutralizi
>95% Control Efficiency for Ethanol
-------
nomic Bi$aael^ResuIt
^/^ ,^>
0 gallons solVmt recovered penvear
r~~/~\ ^~-~~~~~i
,880 saved m annual kacoverv cdst
00 to install Cond^orb^y;
ซ$>
*ayback Schetttile
plus >95% control ofJVfethanol
-------
What is Zeolite?
M & W Industries
Il Approximately 70 Knb^/ti
Slructtires
illiiijl Form, Most Zeolites Tend to be "Hydr(^ii||
act Water
the Chemical Structure, the Zeolite ea||||
e, so tiiey Reject Water. Presently This il
J- : - f - ' - *J - :--::. :.::....:. < ,: -.\y.-.\\ .y.-.yfr.-
-------
Zeolite Molecular Structure
The Basic Structure of Zeolite
is a Tetrahedron
(SI, AL, etc. )O4
Shared Oxygen
Atom at
Each Corner
Tetrahedra Connect at
the Corners to Form
an Open Structure
Silicon or Metal Atom
(NA, AL, etc.)
in the Center
Oxygen at Each
Corner
M & W Industries
-------
Zeolite
M & W Industries
Number of Tetrahedron Controls the Pore Size
Consistent Pore Size Means
- Zeolite can be "Custom Sized" for Specific Solvents, Resulting in
High Efficiency
8.0 A Diameter
-------
Advantages
No Relative Humidity
Control for Some
Applications
100% Regenerable
Guard Bed Upstream of
Zeolite may not be
Needed
Does Not Promote
Chemical Reactions
Inert, Non-Flammable
Material
Zeolite
Higher Replacement
Cost when compared
with Activated Carbon
Disadvantages
M & W Industries
-------
M & W Company Profile
and ft
Initi:
ompany origin;
iricator.
as a mechanical contractor
I activities in air
uses and solvent recovei
control were
svstenis.
xpanded air pollution control equ ipmcnt to
u~\ \ I v \\ P\
include thermal and catalytic oxidizers.
+ 1992i M & Wthe first American company to
carbonrbased(recovery system/io/h zeolite-based
concentratoi^system. This became the Re-Gens
System for/economical VOr destruction.
4 1997: Skxjvent recovery applications addressed when
Condensorb System developed. Combines zeolite
adsorption and mechanical refrigeration.
-------
-- 9
M&WC
/
m evolution c
iosorbT% System for biol
estruction.
ign, fabrication and t
Calblttie Oxidizer
I ;^x
Thermal Oxidizers
Re-GensorbTฅ System
Condensorb7M System
Biosor^b TI^System
Baghquses and Filter Houses
tof
ues with develop
lly-based VOC
-------
rare Manufa
Chemicals
M&W
e Inddstti
4- Commercial Bakin
Pharmaceutical
4- Coatin
Laminati]
i
Semiconductors
-------
A Novel
Fliricfized Bed Concentrator System
For Solvent Recovery
Of High Volume, Low Concentration
VOC-laden Emissions
LU
LU
CC
Edward L. Biedell, P.E.
REECO
Somerville, New Jersey
Presented at the Volatile Organic Compounds (VOC)
Recovery Seminar, Cincinnati, Ohio, September 16,1998
-------
VOC Control Problem
Economically and effectively capture and
destroy or recover dilute concentrations of
VOCs contained in relatively large airflows
emitted by industrial and manufacturing or
other processes.
REECO
-------
Potential Solutions
Thermal Oxidation
- Regenerative
- Recuperative
Catalytic Oxidation
Carbon Adsorption
Hybrid Systems - Pre-Concentrator Followed by
Oxidizer or Solvent Recovery.
ป Carbon Adsorber.
- Fixed Bed Carbon or Zeolite Rotary Wheels.
- Fluidized Bed Adsorber/Desorber Using
Carbonaceous Media.
REECO
-------
Destruction or Recovery?
Consideration Factors:
VOC Composition in Process Exhaust
Value of Recovered Solvent > 300 / Ib.?
Overall Evaluated Cost Comparison
- Capital
- Operating
- Maintenance
CO
q>
LLJ
LU
EC
-------
Fluidized Bed Pre-Concentrator
Applicability
Process Exhaust Volume
10,000 scfm to 500,000+ scfm
VOC Concentration
<300 ppm
Process Exhaust Temperature
Ambient to 120ฐF
REECO
-------
Fluidized Bed Pre-Concentrator
Capabilities/Features
95+% VOC Destruction or Solvent Recovery
- Achievable at Lower Inlet VOC
Concentrations Than RTOs Can
Effectively Handle.
- Solvent Recovery Option Not
Available With Fixed Carbon
Beds or Rotary Wheels.
REECO
-------
Fluidized Bed Pre-Concentrator
Capabilities/Features (Continued)
Very High Air Volume Reduction Factors.
- Typically 800 to 1,000:1
Compared to Fixed Bed or Rotor
Factors of 10 to 30:1.
- Capable of Greater Than 10,000:1.
REECO
-------
Fluidized Bed Pre-Concentrator
Capabilities/Features (Continued)
Cost Competitive With Alternate Technologies.
- Capital Cost
Close to RTOs, Less Than Rotary Wheels
- Operating Cost
Lowest of All Technologies, With
Negligible Fuel Cost and Power Costs
About 20% of RTO, Same or Lower
Than Rotary Wheel
REECO
-------
Beaded Carbonaceous
Adsorbent (BCA) Characteristics
Smooth, Hard Beads
High Surface Area
Carbonaceous Composition
Particle Size Range: 0.3 to 1 mm
<2%/Year Attrition Rate
Capable of On-Site Regeneration
Able to Easily Handle Chlorinated VOCs and HMDS
Without any Adverse Effects.
REECO
-------
Cleaned
Air
Adsorber
From
Process
Influent Gas
Blower
Carrier
Gas
(Steam or N2)
Airlift
Blower
iaSi Condensate
REECO/EC&C Fluidized Bed
Pre-concentrator System Flow Diagram
REECO
-------
Cleaned
Air
Adsorber
BCA
EE3 Contaminated Air
Cleaned
Air
Influent Gas
Blower
Carrier
Gas
(Steam or N2)
Airlift
Blower
REECO/EC&C Fluidized Bed
Pre-concentrator System Flow Diagram
REECO
-------
Potential Industrial Applications
Semi-Conductor Chip Manufacturing Facilities
Surface Coating Facilities:
- Automotive
- Aerospace
- Furniture Finishing
- Metal Decorating
Soil Remediation Sites
Solvent Recovery
REECO
-------
Case Study 1:
...
Semi-Conductor Manufacturer
Air Volume
Temperature
VOC Inlet Loading
Contaminants
Concentrated Stream
Volume
45,000 SCFM
Ambient
10 TO 20 PPMV
IPA
Ethyl Lactate
NMP
Methanol
HMDS
10 SCFM
(4,500:1 Turndown)
-------
Semiconductor Industry
^ ^f
Process:
VOCs (Boiling Pts., ฐF):
Concentration:
Total Emissions:
Slip Stream Tested:
Tests Conducted:
Wafer Fabrication
Acetone (133)
Methanol (148)
Ethanol (173)
IPA (179)
CO
q>
UJ
ill
CC
Xylene (280)
PGMEA (293)
Ethyl Lactate (309)
NMP (395)
N-Butyl Acetate (258) Sulfolane (545)
Hexamethyldisilizane
(HMDS) (259)
0.2 to 250 ppmv
2,000 to 44,000 scfm
400 scfm
Spike Tests
Speciation
HMDS
-------
Semiconductor Process Pilot - Spike Test
Solvents Tested:
Ethyl Lactate
Methanol
Concentrations
Tested, ppmv:
10, 75 & 100
30,100 & 400
Adsorber Capture
Efficiency:
99%
50 to 58%
UJ
LU
CC
-------
REE-9814
VOC CONCENTRATION IN PPMV
1 .4
ro ฃt c> oo o w
_ o o o o o o o
13:26
ST
o
3
o
o
? 13:30
3
2
5T
o
13:34
CO
! H
0) =
r-t- S
a m
13:38
13:42
O
c
ฃ
2.
m
O
CD
0)
0
CD
-------
REE-9814
VOC CONCENTRATION IN PPMV
& 11:53
Q)
h
O
3
o
o
"^ 11:56
O
I-+
0)
U
O
S 11:59
(D
^* ^H
-------
Speciation Test
Speciation test results showing inlet and outlet concentrations, and removal
efficiencies for the four solvents detected. Carbon had been in service 4 months.
Sample
T1-ln
T1-Out
T2-ln
T2-Out
T3-ln
T3-Out
Methanol
Cone.
mg/m3
<0.2
<0.2
0.9
0.5
1
0.4
Removal
Efficiency
N/A
44%
57%
Ethanol
Cone.
mg/m3
22.1
5.7
17.9
2.3
15.7
1.8
Removal
Efficiency
74%
87%
89%
IPA
Cone.
mg/m3
240.5
5.7
222.6
2.3
162.6
1.7
Removal
Efficiency
98%
99%
99%
Acetone
Cone.
mg/m3
71.4
4.5
54.6
1.9
40.7
0.9
Removal
Efficiency
94%
97%
98%
CO
O)
LJJ
ID
o:
-------
HMDS Tests
Issue: Silica Particulate Formation,
Potential Clogging
Tests: 1. Gaseous Injection
2. Liquid Immersion of Carbonaceous
Adsorbent Media Followed by Desorption
Conclusions: 1. No Signs of Capacity Loss or Clogging
2. No Decomposition to Siloxane or
Silicate Forms
3. No Build-up on Fluidized Media, or
Loss of Activity
UJ
LU
o:
-------
HMDS Test Results
Inlet Concentration
1-12 ppmv
38 - 42 ppmv
140-150 ppmv
Outlet Concentration
N.D.
N.D.
N.D.
Removal Efficiency
>99%
>99%
>99%
LU
111
CC
-------
Full-scale Facilities -
Semiconductor Industry
Location
Oregon
Arizona
Oregon
New Mexico
System
Volume
2,000
44,000
20,000
2 @ 4,500 ea.
Start-up
Date
6/94
1/96
3/96
12/96
VOC
Concentration Factor
200:1
4,400:1
2,000:1
1,500:1
ft
CO
LLJ
UJ
o:
-------
Wallpaper Manufacturer - England
Process: Gravure Printing Presses
VOCs: MEK, Toluene
Concentration: 50 to 4000 ppmv
Total Emissions: 89,000 scfm @ 80 F
(9 Presses)
Slip Stream Tested: 200 scfm
Test Duration: 2 Weeks
LU
111
o:
-------
Pilot Test Results -
Wallpaper Printing Emissions
MEK & Toluene -1:1 Ratio
o
o
a.
CL
1200
1000
800
600
400
200
tit
1^
jj$.
"f
t
s
1^
$?
s'**!<*
* if
i^P
<$$$ ^ -^ ^
,
-
>
^
*
1
'.i
>
\\
i'?
^
"* !^i t
'
^1 W ^s -*
IUU
90
80
70
-60
-50
-40
-30
-20
-10
0
3
o
Data Points
Inlet
Outlet
% Removal
LU
LU
cr
-------
Recovered Solvent Composition
Wallpaper Printing Operation
Peak#
1
2
3
4
5
6
7
Chemical
MEK
uPAc
Toluene
Xylene
RT (Mins.)
1.513
1.743
2.097
2.48
3.117
3.403
4.49
Area
0.115
191.536
0.185
188.305
0.282
0.130
0.236
Cone. %
0.000
63.931
0.076
35.967
0.000
0.027
0.000
ai
UJ
cc
-------
Spectroscopic Test Results -
Recovered Solvent Composition
W
0)
D
C
S
v\
-------
Fluidized Bed Pre-Concentration System
Advantages for High Flow-Low VOC
Concentration Applications
High Capture and Destruction/Recovery Potential
Lower Energy Consumption
Smaller Footprint
Reduced Weight
High Reliability
Safety
REECO
-------
Recovery of VOCs by Microwave
Regeneration of Adsorbents
Dr. Philip S. Schmidt
Center for Energy and Environmental Resources
University of Texas at Austin
USEPA/USDOE/CWRT
Seminar on VOC Recovery
Cincinnati, Ohio
September 16-17, 1998
The Problem
Recover VOCs from low-concentration air
streams instead of destroying them
- VOCs a major target of 1990 Clean Air Act.
- Incineration wastes valuable materials and energy.
- Present recovery technologies often not cost-
effective:
ป Direct condensation
ป Hot inert gas regeneration of adsorbents
ป Steam stripping of adsorbents
Possible solution: microwave regenerated
adsorption systems
-------
Advantages of Microwave Regeneration
Facilitates recovery
- Requires little or no purge gas.
- Highly-concentrated off-gas can be easily condensed.
- Does not create liquid separation problem for water-soluble
solvents like steam regeneration.
Enhanced Heat/Mass Transfer Rates
- Heat transfer rate depends solely on available generator power (not
limited by surface area or heating medium).
- Equilibrium process: VOC transport out of adsorbent is dominated
by pressure-driven flow (not limited by molecular diffusion).
- Result: Higher throughputs/Shorter cycle times
Improved Control
- Precise on/off control
- Self-correcting/limiting for some adsorbent/VOC systems
Research Approach
Bench Scale Experiments
- Proof-of-concept, kinetics data, sensitivity to
operating parameters
Process Design Studies
- Configuration alternatives, adsorbent selection
Comparative Economic Feasibility Studies
- Cost-effectiveness in selected applications
Lab Pilot Column and Field Demonstrations
- Scale-up tests, compatibility with commercial
environment
-------
Bench-Scale Experiments
Objective: prove concept, explore desorption
kinetics of MW regeneration.
Tests conducted using stripping gas or under
vacuum conditions (25-150 torr).
Desorbed solvent recovered by condensation.
Materials tested;
- Solvents: MEK, Toluene, nPA, Water
- Adsorbents: MS 13X, Dowex Optipore, UOP
MHSZ
Bed Temperature Profiles:
Conventional vs. MW Regeneration
{Weissenberger 1993)
Temperature Profile Comparison
Conventional vs. 550 Wau Initial Absorbed Microwave-Assisted
20 30
Time (min)
-------
Desorption Effluent Concentration;
Conventional vs. MW Regeneration
(Weissenberger 1993)
Comparison of Effluent Concentration and Temperature
for Conventional and 550 Watt Microwave-Assisted Regneration
1.2 10>
1.0 10*
8.0 10* -
6,0 lO*
4.0 104 I-,1 /
2.0 104
X
MW Regeneration at Low Pressure;
MEK/Dow Polymeric Adsorbent (35 torr)
10 15
Time (min)
-------
MW Regeneration at Low Pressure
Toluene/Molecular Sieve 13X (125 ton)
1
0 R
0 6
0 4
0 2
0
f 'I' ;-1 1 -7-1 1 f T I--T I 1 .... , .,..., POO H
:/ -J : . i 1
/; Temp -: -a
_ /.t.'..'... ..; i - -,onJL
h / : r i : o
. :>- 1 M' 1 ' o^ "
.../. y . : " B
/- /.1 1 !.. H An =
!/ i 1 ! ^ n 5
10 15
Time (min)
20
MW Regeneration at Low Pressure
A Quasi-Equilibrium Process
D)
CD
ฃ
o
O
25
10
I ! i*-^
Vl'n F-iuThr'-
Test 5g (1 W/g)
Tes! 69 (1 Wyp)
t Test 8g (3 W/gj
l*J : M
; T--B,. , : i !
; : "^ir : H
i ; i : ; -I
40 60 80 100120140160180200
Temperature {ฐC)
Negligible Resistances to Heat and Mass Transfer:
Volumetric heating minimizes thermal gradients.
Mass transfer of the VOC out of the adsorbent is enhanced by
a significant pressure-driven flow ("expulsion").
Vacuum minimizes external film resistance to mass transfer.
No nitrogen counter-diffusion.
-------
Process Design Studies
Adsorbent Selection
Vacuum vs. Gas Purge
System Configuration
MW Applicator Configuration
Economic
Feasibility
Adsorbent Selection:
System Performance
Ads. Cost (S/lbmMEK)
Equilibrium Coverage
HeatofDes. (kJ/kg)
Final Reg. Temp. (ฐC)
MW Gen. Power (kW)
Total Cost ($/lbm VOC)
Dow UOP Calgon Davison
Polymer High-Silica Activ. MS 13X
Resin Zeolite Carbon
192 101 17 36
0.13 0.07 0.15 0.07
576 662 752 814
150 193 360 350
298 537 1038 1840
0.207 0.223 0.295 0.445
-------
Adsorbent Selection:
Dielectric Properties (2450 MHz)
p"
fc dry
ฃ"
c sat
Sdry (cm)
Ssat (crr>)
Dow
Polymeric
Resin
0.03
0.24
103
13
UOP
High-Silica
Zeolite
0.03
0.15
120
24
Davison
Molecular
Sieve 13X
0.25
0.25
15
15
Vacuum vs. Gas Purge
Desorption Thermodynamics
Desorption Kinetics
Capital and Operating Costs
- Make-up Inert Cost
- MW Power Requirements
- Refrigeration/Vacuum Power
-------
Vacuum vs. Gas Purge:
Analysis
Final Regen. Temp. (ฐC)
MW Power Consum. (kW)
Recovery System Power (kW)
Total Capital Investment ($)
Total Operating Costs ($/yr)
Make-up Nitrogen ($/yr)
Cost of Power ($/yr)
Cost of Steam ($/yr)
Total Cost ($/lbm VOC)
Vacuum
Purge
120
243
111
3,063,000
472,000
237,000
-
0.206
Inert- Purge
(Heat Recov. )
150
277
100
3,159,000
762,000
260,000
254,000
11,000
0.271
System Configurations
Fixed-Bed Adsorption
- Batch Process
Fluidized-Bed Adsorption
- Continuous Process
-------
Fixed-Bed Systems
BLOWER
Solvent Vapor
Emission
Stream
ADSORBING
DESORBING
BETJ _
^iPRECOOLER
PIVACUUMPUMP
Treated Air
CONDENSER I
CZD
Recovered Solvent
Cooling
Water
Fixed-Bed Column Configurations
ADSORPTION MODE:
REGENERATION MODE:
Axial-Flow
Column
Horizontal
Rectangular-Bed
Column
f-'i-y-::--'*-.*-.'
r-t^-rI
ซ- <
I- '<)>'*"*' " f -'!>'
:S&^
-------
Fluidized-Bed Systems
"'S-K- tit
^-^ JIป
Moving-Bed Applicators
Resonant cavity applicator structures
Multimode applicator
From MW
Generator
Saturated Adsorbent
V
Hot, Dry Adsorbent
-j ^ Saturated
^ ^ Gas
- Dry
Purge Gas
-------
Economic Feasibility Studies
Case Description:
- Industrial Printing and Coating Operation
- Ketone Solvents (MEK, MIBK)
- Cases:
ป PTE: 144,000 cfm @ 500 ppm
ป CC: 22,500 cfm @ 3220 ppm
Incineration Technologies-
PTE Flow (500 ppm @ 144,000 cfm)
Tot Energy (MMBtu/h)
Tot Capital Invest ($)
Tot Oper. Costs ($/yr)
Power ($/yr)
Natural Gas ($/yr)
Total Cost ($/lb VOC)
Case 1
Thermal
Oxid.
92.6
1,664,000
1,800,000
186,900
1,690,000
0.476
Case 2
Catalytic
Oxid.
61.4
2,429,000
1,640,000
137,300
1,110,000
0.433
CaseS
Regener.
Thermal
Oxid.
32.1
3,801,000
902,600
246,000
479,000
0.323
Case 4
Rotary
Concert.
Oxid.
4.2
3,462,000
430,400
111,700
16,000
0.211
Case 7
Fluidized
Bed Ads.
Oxid.
5.7
2,563,000
375,200
189,800
0
0.168
-------
Solvent Recovery Technologies-
PTE Flow (500 ppm @ 144,000 cfm)
Ads. Inven. (Ibm)
Tot Energy (MMBtu/h)
Tot Capital Invest ($)
Tot Oper. Costs ($/yr)
Power ($/yr)
Steam ($/yr)
Total Cost ($/lb VOC)
Total Cost w/ SR Cr.
CaseS
Fluidized
Bed Ads.
Recovery
45,700
6.7
2,563,000
422, 100
164,800
43,700
0.178
(0.032)
Case 9
Fluidized
Bed, MW
Re gen.
38,800
7.7
2,731,000
496,800
255,700
--
0.200
(0.010)
Case W
Fixed-Bed
Steam
Regen.
128,600
8.5
2,042,000
778,400
115,000
127,000
0.205
--
Case 11
Fixed-Bed
Hot Gas
Regen.
49,400
10.4
3,069,000
758,800
257,400
88,000
0.268
0.058
Case 12
Fixed-Bed
MW
Regen.
49,400
7.2
3,099,000
462,100
237,000
--
0.206
(0.004)
Incineration Technologies-
CC Flow (3220 ppm @ 22,500 cfm)
Tot Energy (MMBtu/h)
Tot Capital Invest. ($)
Tot Oper. Costs ($/yr)
Power ($/yr)
Natural Gas ($/yr)
Total Cost ($/lb VOC)
Case 1
Thermal
Oxid-
ation
3.9
507,000
133,300
29,000
58,500
0.046
Case 2
Catalytic
Oxid-
ation
1.7
529,000
127,100
15,200
23,000
0.045
Case 3
Regen.
Thermal
Oxid.
1.2
594,000
87,300
38,000
0
0.039
Case 4
Rotary
Concen
Oxid.
0.4
999,000
113,400
12,100
0
0.059
Case?
Fluidized
Bed
Oxid.
0.9
398,000
79,300
30,000
0
0.031
-------
Solvent Recovery Technologies-
CC Flow (3220 ppm @ 22,500 cfm)
Ads. Inven. (Ibm)
Tot. Energy (MMBtu/h)
Tot. Capital Invest. ($)
Tot Oper. Costs ($/yr)
Power ($/yr)
Steam ($/yr)
Total Cost ($/lb VOC)
Total Cost w/ SR Credit
CaseS
Fluidized
Bed
Recov.
6,200
2.1
398,000
134,900
25,700
32,300
0.042
(0.168)
Case 9
Fluidized
Bed
MW
4,700
2.8
614,000
198,400
93,000
--
0.063
(0. 147)
Case 10
Fixed-
Bed
Steam
36,400
4.8
761,000
314,300
47,100
84,700
0.083
--
Case 11
Fixed-
Bed
Hot Gas
16,500
5.2
1.41-106
399,100
113,500
60,700
0.134
(0.076)
Case 12
Fixed-
Bed
MW
16,500
3.2
1.41-106
237,900
105,600
--
0.099
(0.111)
Pilot Desorption Column
Multimode MW
applicator
Column: 6" glass
process pipe
100-200 Ibm/hr
adsorbent throughput
* 25 Ibm/hr recovered
solvent
3-5 kW microwave
heating rate
-------
Pilot Tests: Key Technical Issues
Validity of process simulation models
- Adsorbent throughput, etc.
Uniformity of heating
Uniformity and depth of regeneration
Purity of recovered solvent
Adsorbent behavior:
- Dowex Optipore
- Rohm and Haas Ambersorb
Controllability
Field Test Unit
Fluidized bed
adsorber/steam regen
system from EC&C
Retrofit with compact
MW desorber unit
LSkWMW
generator
Rated stream flow of
70cfm
Planned field test at
3M site
-------
P " CQiW -1- "?-'-" ' 'A. 'fltarfi V. " .'jJ- ^i11^ ,"*i^-, , --: ' '- 'L ;: '!**. , >i ' ',--., '^/> '-"i. I' '/? n'1!, ; 1 , ,n . "^-"'i 'Htf3i . i' -' -r rr"! ">!1 ' < ,> 'V ' ^ซฃ ^'-' ^i , ' . ; H. VVVL"/ ''77111 -i ' "' ;. "-, ViW?j w L - Jj Wk 1i n1,1 ^fi
r;^y^.a^j.v:?^:f;-V-dfe'H^^tl-s'.n?y
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^fy&W,*J'&^
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-------
-------
REMOVAL AND RECOVERY OF
VOLATILE ORGANIC COMPOUNDS
FROM GAS STREAMS
Hans Wljmans
Membrane Technology and Research, Inc.
Menlo Park, CA 94025
September 16, 1998
Cincinnati, OH
VOC Recovery Seminar
USEPA, USDOE, AlChE, CWRT
-------
Contents
MTR
VOC Emissions
VaporSep Process
Application Example: Polyolefin Production
Conclusions
-------
Membrane Technology and Research, Inc
Company founded in 1983,
dedicated to commercialization of
membrane-based separation technologies.
Novel technologies based on innovative R&D,
funded largely through U.S. government contracts
(Department of Energy,
Environmental Protection Agency)
-------
1995 VOC Emissions in the United States
Source: Environmental Protection Agency
Fuel combustion
0.7 million tons
Other
0.5 million tons
Transportation
8.5 million tons
Industrial Processes
13 million tons
528-F
-------
VOC Emissions for Indus trial Processes in the United State
Source: Environmental Protection Agency
Other
6.6 million tons
Coating/degreasing
operations
3.2 million tons
Chemical/
petrochemical/
pharmaceutical
industries
3.8 million tons
529-F
-------
Commercial Technology: VaporSep
Separates and recovers volatile organic compounds
(VOCs) from air or nitrogen.
First system installed in 1992; currently over 50
systems in operation.
Major application is recovery of monomer in polymer
production operations: PVC, polyethylene,
polypropylene
-------
MTR Multilayer Composite Membrane
Selective
Layer
Microporous
Layer
Support
web
-------
MTR's Spiral-Wound Module
Module housing
Feed flow
Collection pipe (
Feed flow
Permeate flow
after passing throug
membrane
Residue flow
Permeate flow
Residue flow
Spacer
Membrane
Spacer
-------
The VaporSepฎ Process
Membrane
FEED
(HC in Nitrogen)
PERN
IEATE
(HC-enriched)
>- RESIDUE
(HC-depleted)
-------
The VaporSepฎ Process
voc
in air
Compressor
Condenser
Membrane
Liquid
VOC
Permeate
-------
Recovery of VCM from PVC Manufacturing
Problem: Loss of VCM through
PVC reactor purge gas
- Lost material = 700,000 Ib per year
- Emissions restrictions
Treatment alternatives:
- Incineration + HCI scrubber
- MTR VaporSepฎ system
-------
VCM Recovery with VaporSep
Permeate
99% VCM
Condenser
Compressor
Fresh
VCM ~r
Reactor
**PVC product
Condensed VCM
Membrane feed
20 - 70% VCM
Residue
1 - 5% VCM
* To incinerator
Membrane
Knock-out
-------
Vinyl Chloride Recovery Installations
Feed Flow (scfm)
VCM in Feed (vol%)
VCM in Vent (vol%)
Recovery (%)
Capital Cost ($1000)
Plant !
#1 ! #2 ! #3
80 I 20 I 10
35 50 45
2 i 5 I 4
>95 I >90 | >90
150 i 65 I 50
Annual Savings ($1000)** 450 160 I 65
* Capital cost for Plant #4 includes a vacuum pump.
** Annual savings based on 8,000 hours per year and
[ #4 I #5
i 45 I 20
I 40 I 30
I 1 I 3
I >98 I >95
I 300* I 60
I 285 I 80
$0.20/lb.
i #6
I 100
I 60
I >95
I 200
i 900
#7
90
50
20
>80
100
95
I #8 I
I 150 I
i 25 ]
I 3
I >97
i 250
I 575
-------
VaporSep Application Example:
Monomer Recovery in Polyolefin Production
First system installed in 1996 in a polypropylene plant
of DSM, the Netherlands .
Ten additional systems ordered since then.
Process was awarded the 34th Kirkpatrick
Chemical Engineering Achievement Award.
in 1997 (Chemical Engineering Magazine)
-------
Polyolefin Production Process
7 BF'^P * * * '
, aj ซ* *. *
00 O.* ' '
Nitrogen
To flare
(N2, C4, C3, C2)
s
^^^^ipif'
degassin^
pelleting
-------
Membrane Recovery of Hydrocarbons in
Polyolefin Manufacture
Recovered C4, C3, C2
Recycled N2
f '*', '. ' *">'_ *$= j>"'''""
"mv
i ป4 " ' #NV^-\ ^ ^-'^ ^ ^ V*ป' ' *
.. ซ_ m _*_ * >* -- '-^
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DSM Benefits Analysis
INSTALLED COST:
$1,500,000
Operating Costs
Propylene Recovered
$(300,000)/year
$1,100,000/year
NET REVENUE
$800,000/year
PAYBACK LESS THAN TWO YEARS
-------
Comparison of VOC Recovery Methods
100,000
10,000 -
1,000 -
Air
flow
(scfm)
Adsorption
(steam regeneration)
Adsorption
(off-site
regen.)
100 -
0.001 0.01 0.1 1 10
VOC concentration (vol%)
-------
VaporSepฎSystems
60,000
50,000
40,000
Total instated 30>000
VOC recovery
capacity
10,000
0
Waste Reduction Capacity and
Energy Savings Capacity
Installed
Enginee ring jConstruction
3 Total installed
energy savings
capacity
_ (trillion
0
1992 1993 1994 1995 1996 1997 1998 1999
-------
Acknowledgement
We gratefully acknowledge the following U.S. government
agencies for their support of the development of the
VaporSep technology:
U.S. Department of Energy
Office of Industrial Technology
Small Business Innovation Research Program
U.S. Environmental Protection Agency
Small Business Innovation Research Program
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AMERIPURE
Synthetic Adsorbents in Liquid Phase and
Vapor Phase Applications
Presented by:
Steve Billingsley, Director of Engineering, Ameripure, Inc.
VOC Recovery Seminar
September 16-17, 1998 Cincinnati, OH
f'% AMERIPURE
Presentation Summary
* Synthetic Resins
* Typical System Flow Schematics
* Technology Applications
- Liquid Phase
- Vapor Phase
Regenerative Adsorption Systems
-------
OAMCRIPURE
Advantages of Synthetic Resins
Large Surface Area
High Adsorptive Capacity
Physical Integrity
Fast Adsorption/Desorption Kinetics
No Capacity Loss From Repeated Regenerations
Supports Very Little Catalytic Activity
Regenerative Adsorption Systems
f^AMERIPURE
Compounds Adsorbed by
Synthetic Resins
Aliphatic and Aromatic Hydrocarbons
Chlorinated Hydrocarbons
Aldehydes and Ketones
Alcohols and Acetates
Pesticides and Herbicides
Chemical Agents
Siloxanes
Regenerative Adsorption Systems
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f^AMERSPURE
Regenerative Adsorption Systems
Liquid Phase
Adsorbent Bed Design
- Packed Bed
- Up Flow
Synthetic Resins Used
- Carbonaceous
- Polymeric
Steam Regeneration
- Countercurrent {Down
Flow)
Applications
- Landfill Leachate
- Groundwater Remediation
- Wastewater Treatment
- Resource Recovery
Regenerative Adsorption Systems
f^AMERlPURE
Liquid Phase
Schematic
Influen.
* Effluent
Regenerative Adsorption Systems
-------
f^AMERIPURE
Regenerative Adsorption Systems
Vapor Phase
Adsorbent Bed Design
- Packed Bed < 500 SCFM
- Fluid Bed > 500 SCFM
Synthetic Resins Used
- Polymeric
Microwave Regeneration
Applications
- Landfill Gas Clean-up
- Soil Vapor Extraction
- Solvent Recovery
- Vapor Recovery
- Industrial Off-Gas
Regenerative Adsorption Systems
f^AMERIPURE
Advantages of Microwave
No Chemical or Catalytic Activity
Low Water Content in Recovered Product
* Uniform Heat Distribution
Energy Efficiency
Reduced Regeneration Time
Low Operating Cost
Regenerative Adsorption Systems
-------
ฃ% AMERIPURE
Vapor Phase
Fixed Bed Schematic
Effluent
II
Adsorption Desorptton
Influent
Regenerative Adsorption Systems
f~% AMERIPURE
Ameripure Pilot/ Demonstration Trailer
Regenerative Adsorption Systems
-------
AcuvmeO Carson ป a
t^AMERIPURE
MTBE Equilibrium Isotherm
"Traaemarxofltie Dow Chemical Company
All uata are proprietary 10 American Purification. Inc.
25.000 50.000 75.000
MTEE Concentration |mlcrogrimA.i1ar)
Regenerative Adsorption Systems
f^AMERIPURE
Pilot Testing / Proof of Principle
Demonstration
Refinery Site
Influent Concentration 140 - 160 ppb MTBE
Other BTEX / Gasoline Components Present
1250 Gallons at 0.5 GPM
1493 Effluent Non-Detectable (Method 8240)
Steam Regeneration < 5 Gallons
Condensate Concentration 38.7 ppm
Regenerative Adsorption Systems
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AMERIPURE
Pilot Demonstration: Combined Liquid and Vapor-Phase Adsorption
Regenerative Adsorption Systems
;RIPURE
Treatability Study: Pilat Demonstration
US Army Groundwater Site
Influent Concentration 1500 - 2500 ppb Halogenated
Aliphatics (e.g., 1,1,2,2-PCA, TCE, VC)
Treated Approximately 200,000 Gallons at 10 GPM
Carbonaceous Effluent Non-Detectable (Method 624)
Steam Regeneration 80 Gallons
* Utility Costs for System -$0.08 per 1000 Gallons
Total O&M Coste (Utilities, Labor, Disposal) ~$0.74 per
1000 Gallons
Regenerative Adsorption Systems
-------
Field Study: Breakthrough of Vinyl Chloride
Through Carbonaceous Resin
Average Influent Concentration
of 34.4 ppb
**
5000 6000 7000 8000 9000 10000 11000
Bed Volumes
Regenerative Adsorption Systems
Extrapolated Breakthrough of 1,1,2,2-
Tetrachloroethane
0 2000 4000 6000 8000 10000 12000 14000 16CCO 18000 20000
Bed Volumes
Regenerative Adsorption Systems
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=350.000
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[300.000
i
f 250.000
6.200.0X)
c
5 150.000
100.000
o 50.000
Typical Steam Desorption Profile
ฃ0 100 1SO 200 250 300 3SO 400
Tim. (mlnuMป)
:--cis-DCE -ซ trans-DCE:
Regenerative Adsorption Systems
Fixed Bed Vapor Adsorption System
Regenerative Adsorption Systems
-------
f^AMERIPURE
Field Scale System: Service Station
Soil Vapor Recovery System (250 SCFM)
BTEX and Other Aliphatic Hydrocarbons (4.8 Gallons
Recovered per Day]
Recovered Product is Desiccated (7% Water by
Volume) and Delivered to Customers Low-Grade Fuel
Tank for Resale
Utility Costs for System ~$0.15 per Pound of Recovered
Hydrocarbon
Regenerative Adsorption Systems
f^AMERIPURE
Fixed Bed Vapor Adsorption System
Regenerative Adsorption Systems
10
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Field Scale System:
Chemical Process Plant
Currently in Start-Up
250 SCFM Stream
Vapor Recovery (Up to 6 Ibs. Per Hour)
Hexamethyldisiloxane, Trimethylsiloxanol, Benzene,
Toluene
Currently In Data Acquisition Phase
Regenerative Adsorption Systems
f^AMERIPURE
Conclusions
Synthetic Resins Offer Excellent Means of VOC Recovery
Through, Among Other Characteristics:
- High Capacity
~ Rapid Kinetics
Lab-Scale, Pilot-Scale, Full-Scale Data Confirm
Technical Viability and Cost-Effectiveness
Regenerative Adsorption Systems
n
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Cryogenic Condensation for VOC Control
and Recovery
VOC Recovery Seminar
Sept 98
BOC GASES
-------
VOC Emissions
From Batch Chemical Processes
Liquid Nitrogen
Storage Tank
flejil
Typical Nitrogen Blanketing
Applications
Nitrogen Gas
e >
" Storagfe
N2 +
VOC's
-------
KRYOCLEAN VOC CONTROL SYSTEM
LIQUID NITROGEN
STORAGETANK
NITROGEN BLANKETED APPLICATIONS
iiiii
V..liJi* \
7
RECOVERY PRODUCT
BOG GASES
-------
KRYOCLEAN SYSTEM FLOWCHART
HE 200 ON-LINE / HE 300 THAW
HE-20Q On Un$ / HE~300TIi0w
r1--sW&3$l> * *
l^Md%
l^a*ปปซ 6*s
HE**0W Ol^^Jfl^ *?*K"*.-JM*^ ^dRWini ^J **ปsซ*wtป,ซ*-t-r'ปtซrซit ป,, *K*ซ-iซoปtw *,ปซ"-ซcปrjfปi
Hg^3iJ&ThBy# ,;Hฃr3imOfyฃJ^';{ Mg^jfaMSftlf **%l^5^?i
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KRYOCLEAN VOC CONTROL SYSTEM
Nitrogen
Exhaust
Liquid
Supply
Recirculation
Heat Exch.
Ejector
Recirculation Stream
Outlet
Inlet
Process
Heat
Removal
GASES
-------
CONDENSER TEMPERATURE PROFILES
O *H * * ^ * * < ^ "- -u
p. v ป *vV "* ซ -'?-'\ ฐ ','
* ^\." * "%" "^^-**&
-=,' * , < * ,"W-fc?sr
, ^ . ^_ ^i^.'* -.S *^*kJi*^
-------
KRYOCLEAN VOC CONTROL SYSTEM
UNIQUE ADVANTAGE
FLEXIBILITY
Ability to handle increased load
at a high level of compliance
BOC GASES
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KRYOCLEAN VOC CONTROL SYSTEM
Commercial Test Results on Methylene Chloride
20.0
30.25
99.6
-94
-------
Preliminary Test Results
Methylene Chloride Performance
Q.
Q.
ซ*
C
_o
"35
UJ
'S
250
200
150
100
50
85
11
GC
FTIR
88 94 99 104 109
Outlet Temperature, minus Centigrade
BOC GASES
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CASE STUDY
Specialty chemicals manufacturing company needed to control VOC from
storage tanks, including acetone, methanol, heptane, ethyl acetate and
acetic acid
Hired an environmental engineering consultant to evaluate VOC control
technologies on both a technical and economomic basis
Technologies evaluated included:
- Thermal Oxidizer
- Catalytic Oxidizer
- Flare
- Carbon adsorption
- Scrubber
- Cryogenic condensation
-------
CASE STUDY
EVALUATION - Economic
- Methodology used was EPA's Office of Air Quality and
Planning and Standards (OAQPS)
- Accounted for primary control device cost, auxiliary
equipment, instrumentation, freight, foundations supports,
handling and erection, electrical, piping, insulation and
painting.
- Accounted for annual operating costs based on labor rates,
utility costs, costs of consumables, interest rate, control
system life, taxes, insurance and administration.
BOC GASES
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CASE STUDY - ECONOMIC EVALUATION
Technology
Cryogenic Condensation
Catalytic Oxidizer
Carbon Adsorber
(off-site regeneration)
Carbon Adsorber
(on-site regeneration)
Thermal Oxidizer
(with heat recovery)
Thermal Oxidizer
(without heat recovery)
Flare
Annual Cost
$104,000
$169,000
$178,000
$182,000
$261,000
$426,000
$549,000
Capital Cost
$287,000
$220,000
$356,000
$825,000
$305,000
$131,000
$189,000
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KRYOCLEAN VOC CONTROL SYSTEM
SUMMARY/CONCLUSIONS:
Field results of 99-6% recovery at -94ฐF
Lab results of < 10 ppmv at -164ฐF
Potential of cryogenic condensation to cool
VOC laden streams to -250ฐF
Low mist or fog formation due to controlled
surface temperatures
Low operating cost - reuse the vented nitrogen
for blanketing or inerting
Flexibility
GASES
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NUCON International Inc.
Brayton Cycle Systems
For Solvent Recovery
Basic Technology: Low Temperature Condensing
Basic Application: Recover and Reuse. Solvents
Three Specific Cases: Different flows, vapor
concentrations and gas compositions
-------
NUCON International Inc.
RECUPERATOR
COLD GAS
SOLVENTS
J
t
COMPRESSOR
EXPANDER
PROCESS GAS
SOLVENTS
Figure 1 Brayton Cycle Process
-------
NUCON International Inc.
CASE1
TAPE COATING, 3M Greenville SC
Low Concentration, High Flow
Solvent
VOC Concentration, % Vol.
Heptane
0.25
Flow Rate, scfm
7,000
Recovery Required, %
Capital Cost
95
$1.64 million
-------
NUCON International Inc.
EXHAUST
-50ฐF
8 PSIA
O
VACUUM
PUMP
FILTER
HEAT
EXCHANGER SOLVENTS
SLA BLOWER! G
SOLVENT
LADEN
AIR FROM
PROCESS
Figure 2 3M Greenville, SC BRAYSORBฎ Process
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NUCON International Inc.
CASE 2
TABLET COATING, Pfizer, P.R.
Medium Concentration, Low Flow
Solvents
VOC Concentration, % Vol.
Flow Rate, scfm
Recovery Required, %
Capital Cost
MEC12,
MeOH
1700
90
$1 million
-------
NUCON International Inc.
FROM PROCESS
+100ฐF
DESSICANT
BED
DRYER
TO PROCESS PL^
+230ฐF I*
COOLER
i
TURBO
COMPRESSOR
~" COOLER
SEPARATOR
T
SOLVENTS
EXPANDER
-70ฐF
23 PSIA
SEPARATOR
VACUUM RECUPERATOR
PUMP
-150ฐF
^H HHi
6.5 PSIA
Figure 3 Pfizer, P.R. Direct BRA YCYCLEฎ System
-------
NUCON International Inc.
CASE 3
MEDICAL PRODUCT
MANUFACTURING
Carter Wallace
High Concentration, Low flow
Solvent THF
VOC Concentration, % Vol. 10
Flow Rate, scfm 700
Recovery Required, % 99
Capital Cost $1 million
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EXHAUST
FROM PROCESS
SOLVENTS
PROCESS GAS LOOP
HEAT EXCHANGER
FOR PROCESS HEAT
COMPRESSOR
BRAYTON CYCLE
COOLING LOOP
TURBO
EXPANDER
UQ.
COMPRESSOR
Figure 4 Carter Wallace, Indirect BRAYCYCLEฎ Process
-------
Brayton Cycle Systems for Solvent Recovery
Joseph C. Enneking
NUCON International Inc.
Columbus, OH
INTRODUCTION
An innovative technology based on the Brayton thermodynamic cycle was developed and patented
by 3M company and licensed to NUCON International Inc.. The basic premise for the systems
using this technology was that if the temperature of a solvent laden air stream could be reduced
in an energy efficient manner, the solvent would be condensed and could be recovered. Use of a
turbo expander to achieve low temperatures is such an energy efficient method.
The path from a technical concept to installed solvent recovery equipment was a difficult one.
Practical application of this basic cooling method required different process designs for different
inlet conditions. Equipment has been successfully designed and operated for a variety of different
VOC laden streams containing a range of solvents. Application of this technology has involved
low concentrations, below the lower flammable limit for combustible solvents, medium
concentrations around 1% by volume and concentrations in low flow streams as high as 10%.
Reverse Brayton Cycle Process
The basic process used to reduce the temperature of a VOC laden gas stream is shown in Figure
1. The process gas stream enters the turbo compressor which is connected to a shaft common to
the expander. The gas is precooled in a heat exchanger (recuperator) and flows into the expander.
The isentropic expansion results in a large temperature drop and the cold gas is then used to
precool the incoming gas in the recuperator. The condensed solvent is separated in vertical
cylindrical vessels fitted with mist eliminators and is drained to storage.
The pressure change required to provide expansion can be developed by a compressor on the inlet
side of the process or a vacuum pump on the outlet side. It is also possible to direct drive the turbo
but the very high rotation rates (up to 80,000 rpm) require complex and expensive gearboxes.
This basic process can be applied to a wide variety of solvent recovery or pollution control
applications. However, different inlet conditions of solvent type and concentration and air flow
rates along with different emission control requirements call for different process schemes for the
equipment.
Page 1
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Case 1, 3IVI Greenville, SC, BRAYSORBฎ System
When the concentration of VOC's in the inlet air stream is below about 5,000 ppmv, which is the
case for most flammable solvents used in commercial applications, a concentrator is needed before
the condensation process can be effective. Such a system is shown in Figure 2'.
The inlet air stream at this location, at an flow rate of 7,000 scfrn, contains about 2500 ppmv of
heptane. The system contains its own blower to force the air through the activated carbon beds
where relatively high resistance to air flow is developed. Paniculate matter is removed by a
medium efficiency filter. The filter housing also contains an activated carbon bed to remove high
boiling point vapors. The air stream is then passed through the carbon beds to remove the solvent
from the air by adsorption on the activated carbon. The diagram shows flow into and out of the
#2 adsorber through the white valves. The clean air is exhausted to atmosphere. When a bed
becomes saturated with heptane, it is taken offline for regeneration. After inciting with nitrogen,
the gas is circulated through the Brayton cycle process where the expander reduces the temperature
to condense the heptane and the compressors heat the lean gas to remove the heptane from the
carbon (Bed #1, Figure 2.) This closed loop process is continued until the heptane is removed
from the carbon bed. The same closed loop process is used to cool the bed before it is returned to
the adsorption mode. The use of two beds in this system permits continuous operation.
In this process configuration, the liquid solvent is condensed and separated at a temperature of
-20 ฐF and atmospheric pressure. While the heptane concentration is fairly high under these
conditions, very little is adsorbed on the carbon because of the high temperature (350 ฐF). The
residual amount of solvent on the bed at the end of the heating cycle is less than 5% while the
capacity of the carbon to hold solvent during the adsorption cycle is over 25%. Therefore, the
carbon has a fairly high working capacity. This process achieves over 95% recovery of the
heptane which is then recycled to the manufacturing plant.
The system was supplied as two skids containing all the process equipment, two adsorber vessels
and an assortment of piping and valves. The cost of the equipment was $1,240,000. Since most
of the process equipment, piping and valves were preassembled on the skids, the installation costs
were very low at $400,000. This included a building to house the instruments and control systems
and all utilities (nitrogen, steam, compressed air, fire water and the solvent laden air ductwork.
The operating costs amount to about $.07/lb of recovered solvent. Since the system operates
automatically ,little or no operator supervision is required..
Page 2
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Case 2 Pfizer, Puerto Rico, Direct BRAYCYCLEฎ System
One of the process designs used for condensation of solvents from an air stream is the low pressure
version of the Brayton cycle condensing process. One example of the basic design is shown in
Fig. 4\ The solvent-laden air (SLA) enters the process and is cooled in a shell and tube heat
exchanger. The SLA is then compressed in the turbo compressor and passes through an after
cooler. The small quantity of water condensed under these conditions is separated and drained.
In order to prevent freeze-up in the low temperature section of the process, the SLA is then passed
through a desiccant bed dryer. The next step is the pre-cooling in the recuperator. The liquid that
is condensed is then separated from the air. The SLA then passes into the turbo expander and the
cold air then passes back through the recuperator and through the vacuum pump which provides
the flow energy for the process.
This particular system processes 1700 SCFM of air containing about 1% methylene chloride and
methanol. In this case, over 90% of the air is being recycled to the process. Since it is not
necessary to achieve maximum condensation, the more energy efficient vacuum process was
chosen. The condensing temperature, in the outlet from the recuperator, is -90ฐF. The relatively
small vents from 3 units at this location is treated in a small steam regenerated activated carbon
system. The overall efficiency is greater than 98%.
This system was also supplied preassembled on skids. A unique feature of the design was piped
in spare compressors and turbo expander/compressors to provide immediate backup in case of
failure. The capital cost of the equipment was approximately 5800,000 with installation costs of
$300,000. As is the case at 3M, the automatic system requires only monitoring by the operators
of the manufacturing equipment along with periodic minor maintenance. The turbo units have not
been replaced in over 6 years of service.
Case 3, Carter Wallace, Indirect BRAYCYCLEฎ System
For another site, recovery of solvent at about 10% by volume in a nitrogen stream was desired.
The removal efficiency required was 99%. Since the cooling and condensing loads could not be
supplied by the small process gas stream, an indirect Brayton cycle system was designed (see
Figure 7).
The process loop flow is about 500 scfm and contains about 10% by volume of solvent. The
recirculating cooling gas stream (nitrogen) is 3500 scfrn. The high pressure version of the Brayton
cycle process was chosen to reduce the size of the equipment. The Brayton cycle portion of the
process needs no dehumidifying or separation equipment because the gas stream is dry nitrogen.
The final condensing temperature of-75 ฐF reduces the solvent concentration to less than .05% by
volume.
Page 3
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Energy costs are reduced by two features of this process. The hot nitrogen from the compressors
in the utility stream heats water that is used to provide some of the heat required in the process
dryer. In addition, the cold process gas from the condenser is used to precool and condense solvent
in the inlet stream.
This system was supplied on a single skid 8' wide by 27' long by 9'6" high. The equipment cost
was $850,000 and the installation, which was simpler than previous examples, was only $ 150,000.
Conclusions
The same basic Brayton cycle technology can be applied to a variety of VOC recovery
applications. (See Table 1). Custom designed processes have successfully met the recovery and/or
emission control requirements of several industrial situations.
Page 4
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Table 1 Summary of operating Conditions
Client
Solvent
VOC Concentration, % Vol.
Flow Rate, scfm
Recovery Required, %
Total Capital cost, $million
3M
Heptane
0.25
7,000
95
1.64
Pfizer
MeCl2, MeOH
1
1700
90
1
Carter Wallace
THF
10
700
99
1
Page 5
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RECUPERATOR
COLD GAS
SOLVENTS
COMPRESSOR
J
t
EXPANDER
PROCESS GAS
SOLVENTS
Figure 1 Brayton Cycle Process
Page 6
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FILTER
EXHAUST
-50ฐF
8 PS1A
350ฐF
AR
BE
#
\
BON
:D
s
\
A
^
r 1
k A
f
k.
^M
^ x
CARBON
BED
#2
k )
c>
r^
c
VACUU
PUMP
^1
^ ^
1
COOLER
HEAT
EXCHANGER SOLVENTS
SLA BLOWER
SOLVENT
LADEN
AIR FROM
PROCESS
Figure 2, 3 M Greenville, SC BRAYSORBฎ Process
Paee 7
.ee /
IB
-------
FROM PROCESS
+100ฐF
COOLER
DESSICANT
BED
DRYER
TO PROCESS
+230ฐF
COMPRESSOR
"^ COOLER
VACUUM RECUPERATOR
SOLVENTS
-150ฐF
mm m^m
6.5 PSIA
Figure 3, Pfizer, Puerto Rico, Direct BRAYCYCLEฎ System
PageS
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EXHAUST
FROM PROCESS
SOLVENTS
PROCESS GAS LOOP
HEAT EXCHANGER
FOR PROCESS HEAT
COMPRESSOR
BRAYTON CYCLE
COOLING LOOP
TURBO
EXPANDER
COMPRESSOR
Figure 4, Carter Wallace, Indirect BRAYCYCLEฎ Process
Paee9
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VOC Recovery Seminar: Cincinnati, OH
September 1998
CONTROL VOCs IN REFINERY
WASTEWATER
Mike Worrall
Amcec Inc.
Lisle, IL
-------
VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
AROMATIC SOLUBILITIES
IN WATER
Benzene ISOOPPMw
Toluene 470
Ethyl Benzene 150
Xylenes 150
Mike Worrall
Amcec Inc.
Lisle, IL
-------
VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
NESHAPS and Wastewater
Above 10 metric tons/yr:
must be controlled
: less than 1 PPMw in Wastewater
: at least 98% captured/destroyed
Mike Worrall
Aracec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
SOURCES OF REFINERY
WASTEWATER
Desalter
Aromatics units
Chemical units
General Process area
Mike Worrall
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
TYPICAL REFINERY
WASTEWATER
Flow 100 to 2000 GPM
Benzene 50 PPMw
T.E.X. 50 PPMw
Mike Worrail
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
500 GPM CONTAINING
50 PPM BENZENE
54 TONS/YR
MUST BE CONTROLLED!
Mike Worrall
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
CONTROL TECHNOLOGIES
Desalter Emulsion Breaker
Low Capital Cost
Low Operating Cost
Limited impact
Mike Worrall
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
CONTROL TECHNOLOGIES
Activated carbon - liquid phase
Low Capital Cost
High Operating Cost
Spent carbon returned to Kiln
Mike Worrali
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
CONTROL TECHNOLOGIES
Steam Stripping
High Capital Cost
High Operating Cost
Mike Worrall
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
CONTROL TECHNOLOGIES
Air stripping
Moderate Capital Cost
High Operating Costs
Safety concerns
Mike Worrall
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
IMPROVED PROCESS
AMCEC BRU
Nitrogen Stripping
: Solves Safety issue
: Reduced fouling risk
Vapor Phase Carbon Adsorption with
Insitu Regeneration
Mike WorralJ
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
AMCEC BRU - Case Study
500 GPM Wastewater
50 PPM Benzene
50 PPM TEX.
Mike Worrall
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
AMCEC BRU: Case Study
Steam
15001bs/hr
Power
50 Kw/hr
Nitrogen
300 SCF/hr
Equipment
Cost
$1,250,000
Mike Worrall
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
HYDROGEN SULFIDE
500 GPM Wastewater
50 PPM Benzene
50 PPM TEX
25 PPM Hydrogen Sulfide
Mike Worrall
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
AMCEC BRU
12 Systems operating
100 to 3000 GPM
Effective
Reliable
Mike Worrall
Amcec Inc.
Lisle, IL
-------
VOC Recovery Seminar: Cincinnati, OH - Sept. 1998
I
(coal based carbon at 25ฐC)
100
Relative Humidity (RH), %
Mike Worrall
Amcec Inc.
Lisle, IL
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VOC Recovery Seminar: Cindnnat,, OH -Sept. 1998
NITROGEN
MAKE-UP
WASTEWATER
FEED INLET
\
I.
NITROGEN
STRIPPER
CLEAN WATER
OUTLET
CAUSTIC
CAUSTIC SCRUBBER
NITROGEN
PURGE
BLOWER
AMCEC BRU - BTEX and H2S
BTEX
CONDENSATE
RECYCLE TO FEED
Mike WonaSl
Amcec Inc.
Lisle, IL
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MAKE-UP
WASTEWATER
FEED INLET
u:
NITROGEN
STRIPPER
CLEAN WATER
OUTLET
CARBON
ADSORBERS
: Cincinnati, OH-Sept. 1998
BTEX
NITROGEN
PURGE
BLOWER
CONDENSATE
RECYCLE TO FEED
AMCEC BRU - BTEX
Mike WorraH
Amcec Inc.
Lisle IL
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*ttitt.&tt&&ttQttttป^^
CONTROL VOCS Ire REFIretRY WASTEWATER
Paper |jiซseiUed at iiie uSEPA VGC Recovery Saminar - Cincinnati, OH -Sept. 1998
Oil and water do not mix, like many of life's one-
liners this statement is basically true but not the
whole story. Many hydrocarbon liquids, particularly
aromatics, have significant solubilities in water:
Benzene
Toluene
Ethyl Benzene
Xylenes
1800 PPMV
470
150
150
Petroleum refineries do not like salts in their
feedstock since these corrode and foul process
equipment. The first refining step is Desalting where
a hot water wash extracts the salts. If feedstock
contains aromatics then some will be in the desaiter
effluent and this is a major source of refinery
wastewater containing VOCs.
Usually the desaiter is the major source of
contaminated process wastewater and typically also
has the highest BTEX content. At several relineries
the desaiter effluent flow has been as high as 50%
of the total wastewater flow and over 70% ot total
BTEX discharge.
The environmental community is concerned about
releases of VOCs and HAPs (Hazardous Air
Pollutants) to rivers and streams, to groundwater
sources, as well as to the atmosphere. Since
aromatics, such as benzene, are considered potential
carcinogens, they have received considerable
regulatory attention, and are classed as HAPs as well
as VOCs. The National Emission Standarus ior
Hazardous Air Pollutants (NESHAPs) require that
discharges containing more than ten metric tons per
year of a HAP, such as benzene, are subject to
regulation - that's an average of only 2.5 Ibs/hr:
above this threshold stringent levels of control are
required. If other HAPs are also present then ihese
also have to be controlled. For benzene discharges
regulators require control device efficiencies
exceeding 99%.
Other processing units are also sources of aromaiics
in the process wastewaters. Chemicals units
producing aromatics being prime examples.
closed-loop vapoi recovery unit reduces hap/voc emissions at
hawaiian refinery
Aromatics are totally soluble in other hydrocarbons
and only partially soluble in water. Typical benzene
in water levels are 20 PPMW to 200 PPMW, and
uependem on feedstock other aromatics may be
present in similar amounts.
The main eti'luent treatment facility often includes an
activated sludge unit where bio-degradation converts
the final traces of aromatics and other HAPs in the
wastewater to carbon dioxide and water.
NESHAPs do not permit open process drains since
HAPs could evaporate into the atmosphere prior to
reaching the wastewater treatment facility. So it is
necessary 10 provide separate closed drainage
systems for HAPs contaminated wastewater. As
enclosure OT drainage systems is extremely
expensive me HAP treatment unit is often located
adjacent to trie HAPs source.
Just as refineries vary in size so do HAP
contaminated process waslewater flows: from 100
GPivi ai a small refinery to over 3,000 GPM at a
large complex. A 500 GPM flow containing 50
PPMW benzene is an annual benzene discharge of
54 tons and therefore subject to regulation.
There are several techniques available to prevent or
control HAPs and VOCs in wastewater discharges:
[iiese :-*re described ana evaluated below:
-------
Desalter Emulsion Breaker: The desalter water
wash produces an emulsion that holds more benzene
and other aromatics than water and if the emulsion is
discharged with the washwater it increases the
aromatics discharge. Desalters use Heat, electrical
fields and demulsifiers to minimize the emulsion.
Dependent upon feedstock chemistry ii can ue
advantageous to increase demulsifier usage or
change demulsifiers to reduce the amount of
emulsion discharge. One recent trial reported mat
changing demulsifier reduced benzene discharge by
50%.
Activated Carbon: Direct treatment ot the
wastewater with activated carbon reduces aromatics
content to below acceptable limits. In audition, Die
carbon also captures oil, grease and other oryanics.
Working capacity of carbon in the liquiu phase is
about 5% of carbon weight - the spent carbon is
returned to the carbon factory for high temperature
kiln regeneration and reuse. Although effective, me
operating costs are high. One study found that to
treat 500 GPM of wastewater entailed $250,000
capital cost and annual operating costs exceeding
$1,200,000 (freight to/from kiln, kiln fuel, carbon
make-up, etc.).
Steam Stripping: Bringing wastewater to the boil
by live steam injection effectively strips voiatiles
such that discharge contains less than 0.5 PPiviW
aromatics. If overheads condensate comprises equal
amounts of aromatics and water they will piiซse
separate: with over 95% of the hydrocarbons in
upper phase which recycles to the refinery leedstock.
Aqueous phase, with solubility levels of organics,
recycles to stripper for cleanup.
Steam stripping has several concerns: fouling of
equipment with oil/grease: fouling of packing with
salts, particularly those that precipitate at stripper
operating temperatures: energy consumption, even
with 75% heat recovery a 500 GPM unit requires
25,000 Ibs/hr of steam: capital cost is substantial
since stripping column diameter exceeds 1C I'eei.
Air Stripping: Stripping wastewaler with air is vuiy
effective and readily reduces total BTEX to less u>an
the required 0.5 PPMW, Air stripping is best at
around 100DF. As temperature drops packing height
increases - at 60ฐF required packing height doubles
to attain same discharge. Typical stripping air
discharges contain 500 to 3000 PPMV aromatics and
environmental regulations require aromatics capture
before air is discharged. The VOC laden stripping air
is passed through vapor phase carbon which retains
the organics allowing cleansed air discharge. Noic
that, in the vapor phase, carbon hoids several
the quantity of VOC held by liquid phase c
There are two carbon options: off-site or on-site
regeneration. Off-site regeneration entails shipping
the VOC laden carbon to a kiln for high temperature
regeneration. On-site regeneration entails live steam
jesorption ot the carbon - usually a bed requires
sieamuut once a shift.
Areas oi concern for air stripping are; safety, since in
refinery upset conditions large quantities of
Hydrocarbons may gei into ihe wastewater resulting
in explosive conditions in air stripper and vapor
pfiase treatment unit: fouliny of air stripper packing
with oil/grease: fouling of packing with compounds
thai precipitate, particularly those that react with
oxygen: fouliny of carbon by hydrogen sulfide, note
that in an oxygen free situation carbon has very
liniiteu capacity lor hydrogen sulfide, however,
psesence oi oxygen enables chemisorption onto the
jarbun as elemental sulfur that fouls the adsorption
ijures thereby decreasing capacity for aromatics and
outer VOCs.
An iniprovetiieiu Itas Deen developed that utilizes
the advantages oi air stripping and addresses
it.? concerns iisteci above. The improvement was
conceived and patented by Texaco who worked with
the carbon adsorption systems engineers of AMCEC
to develop lull scale units which AMCEC provides on
an exclusive worldwide basis.
iNitroyirn is used as snipping gas thus inerting the
process. Since oxygen is not present the safety
issue is answered. Lack of oxygen (typically now
vveii utfiuw 'i%) inhibits many concerns about salt and
oiner iculants precipitating on to packing, particularly
biological slime formation. Also lack of oxygen
reduces cnemisorpuon of hydrogen sulfide onto the
carbon thereby extending its working life. Obviously
nitrogen is expensive (a 500 GPM wastewater flow
requires a stripper gas flow rate of about 2,000
SCFivl) therefore, the cleansed gas from the carbon
beds is recycled to the stripper.
Oil-site regeneration was selected. Live steam is
i.seu fur regeneration in such a manner that carbon
,esseis (Adsorbers) are not isolated from the
nitrogen stripping loop with the subsequent need to
purge with nitrogen after each stearnout to ensure
mat oxygen is not present. On-site regeneration also
avoids trequent transportation oi spent carbon to the
Kiln for reactivation.
Since system is a Recovery process it is considered
a process unit and therefore does not require the
stringent permitting associated with hazardous waste
units. Thus a win-win process has been developed.
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improved process now known as anicec biu (benzene recovery unit)
NITROGEN
MAKE-UP
WASTEWATER
FEED INLET
CLEAN WATER
OUTLET
BTEX
NITROGEN
PURGE
CASE STUDY
About a dozen BRU systems are operational at
various refineries. A typical system is described
below:
CONDENSATE
RECYCLE TO FEED
WATER-ADSORPTION ISOTHERM
(coal based carbon at 25eC>
Wastewater Flow
Temperature
BTEX
Hydrogen Sulfide
Required BTEX removal
500 GPM
90 to 13QIJF
100 PPIVIW
0 to 5 PPM
to < 0.5 PPMW
O.4
0.3
HAP contaminated wastewater from an API
separator is pumped into stripping tower and
descends through 20 feet of high efficiency packing -
2.5" diameter polyethylene open type spheres. The
stripped water discharges with less than 0.5 PPMW
BTEX so meeting the water discharge regulations.
Nitrogen circulates at 2000 SCFlvl so that BTEX
concentration at top of stripper is aooul 2200 FPiviV.
Nitrogen temperature equalizes to that oi incoming
wastewater and exits stripper at 100% relative
humidity (RH). For effective carbon adsorption Hie
VOC laden gas (VOCLG) must be at less than 50%
RH and as cool as practical.
Adsorption is temperature sensitive and carbon
rapidly loses working capacity above 120UF.
Moisture content of the VOCLG is important as will
be seen from the graph:
0 20 40 60 80
Relative Humidity (RH). %
Wim RH levels below 40% carbon has a slight affinity
ror water. Above 60% RH the capacity to hold water
increases tenfold and water is attracted to the same
adsorption sites as organic compounds. Because of
me vast uitierences in heats of adsorption between
v-;aiwr utiu organics (1350 compared to 140 BTU/lb),
it is not possible lu displace water with an organic
unless substantial external energy is provided. Thus
wilh high RH conditions carbon may become "water
logged" and unable to capture organics. Therefore,
VOCLG is cooled to about 90ฐF which condenses
much ot the water vapor. After demisting VOCLG is
heated to 115UF lowering RH to 40%. Thus VOCLG
enters carbon at a suitable temperature and RH for
eneCiive adsorption.
-------
Two carbon beds are provided - each bed sized to
adsorb for an eight hour shift at full incoming BTEX
load. The carbon bed captures more than 99% of the
BTEX so the nitrogen recycled to the stripper
contains less than 20 PPMV. The stripper had been
sized to operate with 50 PPM BTEX in the nitrogen
stripping gas so the 20 PPMV does not upset
stripping performance. While one carbon adsorber
captures BTEX the other is being counier-lluw iive
steam regenerated. Desorption steam displaces me
nitrogen in the adsorber being regenerated pushing it
through the condenser into the main nitrogen loop -
raising loop pressure from 2 PSIG to 7 PSIG which
does not impact stripper or adsorber performance
and avoids loss of nitrogen. Steam slowly heats the
carbon bed to about 230ฐF releasing much ot the
adsorbed BTEX. The steam/BTEX vapors flow to a
heat exchanger for condensation and cooling.
Provided steam flow is within the condenser size and
coolant flow there is no passage ol steam or BTEX
vapor past condenser and into main nitrogen loop
At completion of desorption steam Mow ceases cmd
as steam in desorbing vessel cools, nitrogen is diywn
back through the condenser from the main nitrogen
loop. This reduces loop pressure back to 2 PSiG.
Desorbed vessel is cooled by a slip stream flow of
nitrogen from main loop, after 30 minutes bed is
sufficiently cool for return to adsorption service,
Regeneration is completed within 4 hours so the
adsorber is then parked in standby mode until me on-
line adsorber needs to be regenerated. Ttie long
idle period permits the BRU system 10 nanale
substantial surges in VOC inflow ana also
accommodate some loss of carbon activity without
upsetting overall system performance. An analyzer
monitors the nitrogen leaving the carbon bed lor
VOC content and will initiate early desorption of the
adsorber if it is overloaded.
Condensed steam and BTEX are decanted into
organic and aqueous phases. Organic layer is
pumped to refinery feed. Aqueous phase, containing
about 1000 PPMW organics, is pumped into
wastewater feed entering the stripper.
Steam consumption is around 1500 ibs/lir. Eieurie
power including that for the air cooled
dehumidification and desorption condensing units,
but excluding wastewater pumps, is about 50 Kw.
Nitrogen consumption is about 5 SCFM which is
mainly used by the blower shaft seals.
Capital cost for equipment and controls built 10
refinery standards, excluding foundations and
installation, was about $1,250,000.
Operating experience has been good wiui liiile
system downtime. Carbon beds (each 5,000 Ibsj are
replaced every six to twelve months, as pores are
fuuleu by higher boiling compounds and elemental
sulfur troin the chemisorption of hydrogen sulfide.
Refinery wasiewaier entering the BRU has passed
through an API separator and a dissolved air
floatation unit so minimizing oil and grease content.
Nevertheless on one or two occasions the BRU has
received quantities ot oil that temporarily coat the
stripper pacKiny reducing its performance. Within a
iew hours the waslewater washes the packing clean
restoring iuil perlonnance.
HyuiU^eii SuUicie: at facilities where there is a
constant hydrogen sullide load of more than a few
PPlVi it is advisaDie to' add to the BRU treatment
train. One sucli project had about 25 PPM hydrogen
sulfide in the wastewater (6 Ibs/hr in 500 GPM).
Refinery wanted most of the H2S removed and it was
preferred that the period between changeout of the
itfyenerubie caibun bed be at least six months.
Most ul tiie H:.S strips out with the BTEX. The
VOCLG then passes to a caustic scrubber where
musi 01 tne H-,3 is captured by the scrub liquor.
Scruu liquor is a 10% sodium hydroxide solution
enroute LO another process unit: so the caustic
solution only made one pass through the scrubber
belore discharge to tne other process unit. After
scrubbing trie VOCLG passes through a guard bed of
impregnated carbon before entering the regenerate
carbon adsorbers. The impregnated carbon
cneinisorbs most or the remaining H2S - bed is non-
uie and is replaced every six months.
summary Hie BKU system lias proven an
aive aiiu uepenuabie means to remove BTEX
s* wusiewaitffs answering the safety
is ut reiinery people, yet compared to the
auei natives, itas low operating and capital costs.
A British educated engineer with over 30
experience in the design of carbon
systems fur industrial clients
ite is Vice President of AMCEC inc.
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Separation of Volatile Organic
Compounds from Water
by Pervaporation
R.W. Baker
Membrane Technology and Research, Inc.
-------
Feed
liquid
Purified
feed
n
Condenser
Condensed
permeate
liquid
-------
< 1 ppm toluene
Purified feed
Feed liquid
500 ppm
toluene
n
Condenser
Condensed
permeate liquid
5-10% toluene
-------
3,000
2,000
Separation
factor
(Rpervap)
1,000
0
TCE
Ethyl Acetate
1-Propanol
20 40 60 80 100
Feed velocity (cm/s)
-------
Stagnant
mass-transfer
boundary layer
Selective
layer
Cu
**b r-^.
1 L U J i
Turbulent
well mixed
bulk solution
6
^
ป
^
^ *
P-*
mmi
/
^^n>
Porous
^^^ support
^^*^^ layer
^ Permeate
flux
-------
Once-Through Pervaporation
Feed pump
Membrane modules
Heater
^ Treated
water
Condenser
Permeate
discharge
-------
Batch Pervaporation
Feed
1
Surge tank
-ซ*H
Feed tank
Heater Membrane
modules
Filter
IAN
Feed
pump
Drain
treated
water
Condenser
Permeate
discharge
-------
Percent of toluene
remaining in feed
0.1
0
t
Start
50
100
150 200
1 t Time (min) ' I
Start
Stop
Discharge-fill
250 300
Start
Stop
Discharge-fill
350
Stop
-------
Applications
Food and Flavor Recovery
Fine Chemicals/Process Streams
Pollution Control
- Groundwater
- Industrial Wastewater
-------
Peppermint Oil Decanter Run-Off
Feed
12.425
1.515
Stop
A_
J I I 1 1 1 1 L
246
8 10 12 14
(min)
16
Permeate
(diluted 20-fold)
6 8 10 12 14 16
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Photographs of the MTR batch pervaporation
system installed at DOE's Pinellas field site.
-------
1,000,000
100,000
10,000
MeCl2
concentration
(ppm)
1,000
100 r
Permeate
Separation factor
Elapsed time (min)
10,000
1,000
100
Separation
factor
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1,000
100
Flow
(gpm)
10
0.1
Air stripping/
carbon
adsorption
0.001
0.01
Steam stripping
Pervaporation
Off-site disposal
j i
0.1 1
VOC concentration (%)
Distillation/
incineration
10
100
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A Plug for the Sponsors
Department of Energy
Basic Energy Sciences
Environmental Protection Agency SBIR Program
(Pilot system built)
Department of Energy Office of Industrial
Technologies
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Dehydration & VOC
Separation by Pervaporation
for Remediation Fluid
Recycling
Leland M. Vane, Ph.D.
United States Environmental Protection Agency
National Risk Management Research Laboratory
Cincinnati, Ohio
Pervaporation: Permeation & Evaporation
VOC Removal
Liquid Vapor
VOC-Selective Membrane
(Non-porous)
Water
VOC
Dehydration
Liquid
Vapor
Water-Selective Membrane
(Non-porous)
-------
Pervaporation Process Units
Ruwiiiew
c Membrane
Module
ReeUuaJ
Liquid
In SituSoU Flushing
Flushing Solution
Injection Well
Withdrawal
Weil
Aquifer
Soil Flushing Options
Aqueous Surfactant Solutions
* solubilization
* mobilization
* foam flood
Solvents
* Pure alcohols
* Mixed alcohols
* Alcohol & Water
Mixed Surfactants and Alcohols
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Example of Surfactant Solution
Pilot Demonstration at Hill Air Force Base
Injectate:
* 6 gpm
ป 8 wt% Cytec Aerosol MA80
* 4 wt% Isopropyl Alcohol (IPA)
ป 1 wt% Sodium Chloride
Extracted Fluid:
* 11 gpm
* 4 wt% MA80 Surfactant
* 2 wt% IPA
* 5,000 mg/L VOC: TCE, TCA, PCE
ESTCP Validation Project
Marine Corps Base Camp Lejeune
PCE Contamination at Dry Cleaner
Injectate:
* 0.6 gpm
* 16 wt% surfactant (max.)
* 16wt%IPA(max.)
Extracted Fluid:
* 1.55 gpm
* 5 wt% surfactant (max.)
* 5wt%IPA(max.)
* 10,000 mg/L PCE (max.)
Remediation Fluid Recycling
Surfactant
Salt IPA
-------
Significant Material Savings
for 6 gpm, 8 wt% surfactant injectate
Surfactant Injected
Surfactant Recycled
Surfactant Material
Savings
5,800
Ib/day
5,100
fb/day
89%
Significant Cos! Savings
Surfactant Cost without
Recycle
Surfactant Cost with Recycle
Cost of Pervaporation
Cost of Ultrafiltration
Total Cost with Recycle
Surfactant Cost Savings
$5,800/day
$630/day
$420/day
$58/day
$1,100/day
81%
$4,700/day
assumed surfactant value of Jt.oO/lb
Surfactant Solution May Also
Contain Significant Alcohol
Material and Value
If 4 wt% IPA injected at 6 gpm:
* 2,880 Ib/day of IPA injected
* IPA value of $1,150/day
($400,000/yr)
If 16 wt% IPA injected at 0.6 gpm:
* 1,150 Ib IPA injected each day
* IPA value of $460/day
* ($160,000/yr)
assumed IPA value of 50.40/lb
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Scheme for DNAPL Separation &
Alcohol Recovery
Surfactant
Alcoho!
Water
Surfactant
Surfactant
Alcohol
DNAPL
Water
Water
Alcohol Dehydration
Alcohol
Water
Alcohol
NAPL -
Water
Alcohol
Pervapo ration
System
Water
NAPL
Technical Approach
Bench-scale and pilot-scale
experiments with surrogate
solutions.
Bench-scale modeling of process.
Pilot-scale demonstrations with
actual remediation fluids.
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Surfactant Reduces VOC Availability
50ฐC
01234
Cytec MA80 Surfactant Cone. (wt%)
Mass Transport Controlled by
Liquid-Side Concentration Gradient
Surfactant Solution
Vapor
Boundary Layer
EPA has Evaluated
Pervaporation with Several
Surfactants
Bench-scale:
* Triton X-100 (nonionic)
* Sodium Dodecyl Sulfate (anionic)
Pilot-scale:
* DowFax 8390 (anionic)
hexadecyl diphenyl oxide disulfonate
* Cytec Aerosol MA 80 (anionic)
sodium dihexyl sulfosuccinate
1 with IPA and NaCI as modifiers
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Pilot Scale Spiral Wound and Hollow
Fiber Membrane Modules
Spiral Wound PB^J
1 )
Bundto of CoM*d Fl
Hollow Fiber
Pilot Unit Performance Reduced by
Presence of Surfactant
spiral wound modules, 50 deg, C, 50 torr, 1 gpm
No
Surfactant
1.7wt%
DowFax
Surfactant
0 10 20 30 40 50 60 70 80 90 100
% VOC Removed
5,000 Gal. of SEAR Fluid from Hill
AFB Processed with EPA Pilot Unit
2.5 wt% Cytec MA80 Surfactant
1.5 wt% Isopropyl Alcohol
3,000 mg/L TCE
400 mg/L TCA
400 mg/L PCE
< 100 mg/L other VOCs
trace oil
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VOC Removal from Hill AFB SEAR Fluid
(four 2"x36" spiral wound or two 2"x15" hollow fiber elements')
(0.25 gpm, 40 deg. C, 20 tore, tanker truck feed)
Spiral Wound
Hollow Fiber
0 10 20 30 40 50 60 70 80 90 100
Single-Pass VOC Removal (%)
in collaboration with New Jersey Institute of Technology
Potential Payoff
Payoff of In Situ Soil Flushing
> reduced remediation time
> reduced remediation expenditures
Payoff of Surfactant and IPA
Recycling with Pervaporation
> Material savings
* Cost savings
- > $1,000,000 per year for 10 gpm
installation
Current EPA Work in RFR
Design, construct, and operate field
pervap unit to treat PCE/surfactant
stream at Camp Lejeune.
Consider IPA recovery at Lejeune.
Relate Henry's constants to
surfactant properties & cone.
Model effect of micelles on mass
transport in pervaporation.
-------
I
I
I
1
I
I
I
I
1
I
I
I
I
1
I
I
I
Conclusions
VOC Separation & Recovery
Critical for Cost-Effectiveness
of In Situ Soil Flushing
Pervaporation Capable of
Performing the Necessary VOC
Separations
* VOC-NAPL/Surfactant
* Alcohol/Water
* Water/Alcohol
Acknowledgments
Franklin Alvarez (EPA)
Lynnann Hitchens (EPA)
Eugene Giroux (EPA-SEE)
Sean Liu (EPA-Postdoc)
Kam Sirkar (NJIT)
-------
-------
EPA/USDOE/AIChE/CWRT; VOC REtxwery Seminar, September 16-17, 1998.
Polymeric Resins
for VOC Removal
from Aqueous Systems
Yoram Cohen
Department of Chemical Engineering
and
Center for Environmental Risk Reduction
University of California, Los Angeles
Los Angeles, California 90095
C 1998, Yoram Cohen, UCLA
EPA/USDOE/AIChE/CWRT; VOC Recoveiy Seminar, September 16-17, 1998. gซjj |7i
uttftf^
Outline
[..Tir*ir.i^
piiiiiiiiii^^
piiiiiiiiilmaiiiiilH
iiiiiiiiaiiiSirjpH
C 1998, Yoram
Cohen, UCLA
-------
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
Separation Processes
to the Rescue!
Raw
Material
Products
Clean Water
01998, Yoram Cohen, UCLA
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17, 1998.
Some Application Areas
PJP
i . I*
Adsorption of organics from aqueous
systems
Ion-exchange resins
Organic liquid-liquid separations
Non-adsorbing aqueous size exclusion
chromatography (SEC) resins
Hiw
O 1 998, Yoram Cohen, UCLA
-------
EPA/USDOE/AIChE/CWRT;VOCRecoveiy Seminar, September 16-17, 1998.
Polymer Resins
and Activated Carbon
:*i!;!Highiisiwrface:area^>1000^ ^ ; ^
./.;:Jfn^:;::-...,;-,;-.-;--,..;;:;:;:;r!::;^:::; ;;::i:
*; ;LJpw:heat;pf:adSPrpti6n: : : *:
^ Solvent regeneration *.
(e.g., using aliphatic :
Limited choice and high :;::;:;;
i;;;::!iCPSti(^ii$Mkg>!!!:!!i!:i!::!!i!!ii:!;;::;::;- ;:;i:ii;
ii^i::
PrP
High'isurfiaceiiarea!::;::::!!!;;:;;^.:^:
!(!^!!l;000;;m^g)i;:^!:::-:':::;:::;::;i-;;:;:
High heat of adsorption
;Tll^hiiaIr6^n6raiibih;:;; ;;:;;:;;
(e.g.; steam regeneration).
5%^10% degradation per
Readily available, low cost
adsorbent material :;;;;;
Speriticarbpriimayihave tp;
be treated as hazardous
0 1998, Yoram Cohen, UCLA
EPA/USDOE/AJChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
Adsorption of a Mixture of Chlorinated Pesticides
in a Packed-Bed
sT
O e.o
I
e -.o
S ao
o a-ฐ
Plow nto - Q.1SW opm/(|'
Activated
Carbon
Bed Volume
Source: Fox/ C.R., Chem.Eng.Prog., 75, 70 (1979)
0 1998, Yoram Cohen, UCLA
-------
EPAAJSDOE'AIChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
Major Performance Issues
Resin Characteristics
Solute-Resin Affinity
Mass transfer limitations
Resin regeneration
Long-term stability
O 1998, Yoram Cohen, UCLA
EPA/USDOE/AlChE/CWRT; VOC Recovery Seminar, September 16-17, 1998.
Resin Characterization
distribution
Inaccessible pore yolume and
wettability
0 1998, Yoram Cohen, UCLA
-------
EPAAJSDOE/AJChE/CWRT; VOC Recovery Seminar. September 16-17, 1998
Dependence of the Surface Area of the Polymeric
Resins from the average Pore Size
1200
1000
300
~5>
8 'veoo
II
< 400
200
1 F-400
2 Mn170(com)
3 XAD-4
4 XUS .
5 Mn170(lab)
6 Mn150
7 XAO-16
8 XAD-2
9 XAD-S
10 Reillex-425
11 XAD-12
50 100 150 200
Pore Size (Angstrom)
250
Surface Area
Improvements
ฉ 1998. Yoram Cohen, UCLA
RESIN SURFACE PORE PORE RADIUS ^H
AREA VOLUME (A) ^M
(M'/G) (CM3/G)
F-400 (Activated Carbon)
XAD-2 (SDVB)
XAD-4 (SDVB)
XAD-16 (SDVB)
XAD-8 (Poly(methylacrylate)"
Reillex-425
Polyvinylpyridine-divinylbenzene
Polyclar-AT
Polyvinylpyrrolidone, crosslinked&
XUS (43493. 01)
MN-150
MN-170
1078
353
870
889
126
110
1.2
1100
821
1066
0.652
0.78
1.18
1.75
0.63
0.63
<0.004
1.3
1.01
1.4
14.7
48.3
24.5
39
98
156
<10
23.5
39.9
26
ฉ 1998, Yoram Cohen, UCLA
-------
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17, 1998. CL.F
1 ..*
Macrcpts
Resin
XUS
Mn150
Mn170
XAD-4
XAD-16
tte$' MlOTpcซ^sjiiKl0'lnacce
Atom
(cm2/g)
1100
698
836
845
889
"micro
(cm2/g)
772
554
836
114
71
Vtotal
(cm3/g)
1.30
1.01
1.40
1.10
1.75
_ ., ซ**"
ssfble pore Volume;
"micro
(cnr/g)
0.39
0.30
0.43
0.05
0.02
Vina'Vtotal
(cm3/g)
0.11
0.05
0.31
0.43
0.46
C 1 998, Yoram Cohen, UCLA
Prewetting of Hydrophobic Resins
Methanol
Pore Fluid]
O
o ฐฐ t^-"" ฐo o ฐฐ\
a Cluster of Hydrophobic Air or Vapor
Micro-spheres
-------
EPA/l
JSDOE/AIChE'CWRT; VOC Recovery Seminar, September 16-17, 1998.
Solute-Polymer Affinity
ff
Hanson solubility parameter
approach
* Adsorption and swelling
(absorption)
* Unexpected multi-solute behavior
loc^
0 1 998, Yoram Cohen, UCLA
Selecting the Polymer Phase
Hansen Solubility Map
01998, Yoram Cohen, UCLA
25
10 12 14 16 18 20 22 24 26
Hansen Solubility Parameters:
ฃd: Contribution of dispersion forces
5pi Contribution of polar forces
&,: Contribution of hydrogen bonding
5,=(
hermodynamic Criteria of Solubility:
AGnFAHU-TAS,*
-------
EPA/USDOE/AJChE/CWRT; VOC Recovery Seminar, September 16-17, 1998. fjJi_P
Distance between PVAc and Different Organic Liquids
on Hansen Solubility Map
(For a good solvent, A<5 (J/cm3)1/2 [Krevelen, 1990])
14-
13-
12 -
11 -
C 10 -
n""* 9 -
E 8-
4 -
3 -
2 1
1 i
A>7 Poor Solvents
A<5 Good Solvents
|
I
I
I 1 1 1 1 I
1
I
i
1. Acetic acid
2. Chloroform
3. Cyclohexane
4. Cyclohexanol
5. Cyclohexanone
6. 1,1 -OCE
7. 1,4-Oioxane
8. Ethanol
9. Isobutene
10. MEK
11. Methanol
12. TCE
13. Toluene
1 2 3 4 5 6 7 8 9 10 11 12 13 14
Organic Solvents
0 1998, Yocam Cohen, UCLA
EPA/USDOE'AlChE/CWRT; VOC Recovery Seminar, September 16-17, 1998.
lฃ2 IE3 IE4 IE5 IB
COMCOmUTtON TCE
C 1998, Yoram Cohen. UCLA
-------
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17,199S.
Adsorption of VOCs onto Polymeric
Resins - A Simple Correlation
fJP
lud*
O XAD-4, XAO-2, o XAD-B {rBportorf horeln)
XAD-4, & XAD-7, ltซyซ
a ES 86t Colti UK) Rodriguez, (1982}
. c ^
hซtfve Enซroy Oentlly, (*.- ^f, (olf
O 1998, Yotam Cohen, UCLA
EPAAJSDOE/AIChE/CWRT; VOC Recovery Seminar. September 16-17, 1998.
IOU
oi
w 10"
u
u
o.
10'
- 400
A XAO - *
V XAO - 2
O XAO - 8
o REILLEX 425
10
10'
io2
io
PCS CONCENTRATION (ซ/L)
C 1 998, Yoram Cohen, UCLA
-------
EPA/USDOE/AlChE/CWRT; VOC Reooveiy Seminar, September 16-17, 1998. p. |fc
"lljCl*
ADSORPTION onto POLYSTYRENE XAD-4
FUGACITY INTERPRETATION
10
"?
> to'2
"5
e
5 -3
** 10 3
55
O
E
e 10"*
ฃ
|
P 10~5
o
ง
i io~*
to
10-7
10
O PkMiel T - 82 C
A TCE
9 CHCL
a PCE
o ct^a,
- O ฐ
6
a 8 ซ
0 B ,rf?
ฐป j*^
0 ^B^*^
"^^ *
^b ^ ซซ
0 n * 1
^ a
" ฐ aฐ ^?I* VN-
ฃ& 9
..!.._! ' ' '
a v
q*^" ^'
-ft, V jjfttf
P w
1
**
s
N
-
oo
f
1
n
Q
\
1
c
u
\
- ,ซ- 10-* 10-* w9 w"* ift"* ป"* ""'
.
FUCACITY (atm) (Fugacity=HCw)
O 1998. Yoram Cohen, UCLA
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
Adsorption/Regeneration System
Detector
Effluent
Effluent Effluent
1 a-f Solvent Reservoirs
2 Solvent Select Valve
3 a,b Piston Pumps
4 a,b Higji Pressure Mixer
5 Adsorber column
6 UV Detector
7 SIM Box
S 386&X Computer
O 1998, Ycpram Cohen, UCLA
-------
EPA/USDOE/AJChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
fJF
U*
Cyclic Adsorption/Regeneration Process
O 1993, Yotam Cohen, UCLA
EPAAJSDOE/AlChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
Column Regeneration
(M;
\mM,m^m
. ~*tf . i -.--. ^^A^-L-i
"* ^ A A ^ A T^-* &i-O^V J-V-iฐ ^ > %
O 1998, Yoram Cohen, UCLA
-------
EPA/USDOE/AlChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
Breakthrough Curve for Chlorobenzene in XUS Column
1
Q = 20 ml/min
C=250mg/l
0 200 400 600 800 1000 1200 1400
Bed Volumes
O 1998. Yoram Cohen, UCLA
EPA/USDOE/AlChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
O
O
D
5 10 15
Bed Volumes MeOH
Regeneration Curve
for Fixed-Bed
XUS Column
Saturated
with Chlorobenzene.
C 1998, Yoram Cohen, UCLA
-------
Column efluent concentration C/Cg
4^ < < w n o
itSig*
3 i S t n" i
Fractional recovery
-------
Mass Adsorbed, mg/g
Solute Concentration (g/1)
^ U K> H g f> ^ 30
1 ' * ft -v in
o o oo
oooe
3333
^ -T
fr 01
sg
-------
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
120
100
80
60
40
20
Benzoic Acid
Recovery from
MN-170 column
using a recycled
Methanol Stream
0 5 10 15 20 25 30
Concentration of Benzoic Acid in methanol (g/l)
O 1998, Yorara Cohen, UCLA
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
120
100
>.
80
u
-------
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar. September 16-17,1998.
Solute Recovery and
Solvent Regeneration
FvT
liK**
c. -Sft o --s". N- O.o,^,* ' '% ->'**"
01998, Yoram Cohen, UCLA
EPA/USDOE/AJChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
Resin Stability
C 1998, Yoram Cohen, UCLA
-------
1.10 -
1.09 -
1.08 -
1.07 -
1.06 -
1.05 -
1.04 -
1.03 -
-------
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17, 1998.
1.10 -
1.09 -
1.08 -
1.07 -
1.06 -
1.05 -
1.04 -
1.03 -
1.02 -
s 1.01 -
CT 0.99 -
0.98 -
0.97 -
0.96 -
0.95 -
0.94 -
0.93 -
0.92 -
0.91 -
Resin's Performance for Repeated
Adsorption/ Regeneration Cycles
.
Relative mass of benzoic acid
adsorbed onto XUS resin
over repeated process cycles
0.9U H i 1 1 - r i
0 10 20 30 40 50
Cycle Num her
Ef\l
!
ซ*
i i
60 70 80
C 1998, Yoram Cohen, UCLA
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
Resin Stability
O 1998, Yoram Cohen, UCLA
-------
EPA/USDOE/AJChE/CWRT; VOC Recovery Seminar, September 16-17, 1998.
Mass Transfer Limitations
f-^ V^N>N>\>_
* tf1 v > > "&
'ซv>,%*;v
J> ^? ^-rn-"
*/ J
%>*
s ซ ซ
SV,-o
**y
"*W Vs --\*
O 1998, Yoram Cohen, UCLA
EPAAJSDOE/AIChE/CWRT; VOC Rficovoy Seminar, September 16-17, 1998. .PJ; j
Source Adsorbent
This study Macronet
Huang et al. Macroreticular
(1994)
Takeuchi and Activated
Suzuki (1984) Carbon
IU0
P
LA
Temperature intraparticle
(K) DiffusivityxlO11
[m2/s]
293 1.05
300 2.71
298 0.41
O 1 998, Yoram Cohen, UCLA
-------
EPAAJSDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
SUMMARY
vv3*;*wfii^
X*"i*'i^K,2fjiilฃii&,Vi*-s^^itซi 4feปiir.*lM*Mlw3K<,'V'- -
C1998, Yoram Cohen, UCLA
EPA/USDOE/AIChE/CWRT; VOC Recovery Seminar, September 16-17,1998.
O 1998, Yoram Cohen, UCLA
-------
EPA/USDOE/AIChE/CWRT; VOC Recoveiy Seminar, September 16-17,1998.
-------
-------
-------
-------
The New CPAS
Separation Technology &
Pollution Prevention Information
Tool
Dr. Robert M. Patty, Dir
ictor
The Construction Produfetivitv Institute
EPA Volatile Organic Compounds (VOC)Kecof e
Vernon Manor Hotel, Cincinnati, (Mh
Sept 16-17, 1998
CPI
y Sominar
-------
"The most significant technical barrier
to waste minimization/may be
a lack of suitable engineering information
on source reduction & recycling techniques."
Cheremisinoff & Ferrawe (1989)
-------
There is a large dearth of pertinent infbrmati
and the guidance techniques/to accomplish
source reduction - design process changes
For example, pollution prevention otions
for process effluent streams
already installed by other
are not well documented.
organizations
U.S. Congress, Office of Technology^Assessment (1994)
-------
"If you want to change
person's way of thinking,
don't give them a uectufp,
give them a tool."
Buckminster Fuller
-------
WhatisCPAS?
CPAS is a set of pollution/prevention
process and product design tools
containing design information rega
new and existing clean technolog
and design for constructabili
rding
ies
-------
The Separation Technologies
Pollution Prevention Information
is one CPAS to
A relational knowledge base in which project te&ms
identify viable pollution prevention options during
by-stream analysis of process facilities.
These tools include 518 new or emerging sourc
reduction, recycling, and end-of-pipe\treatment
technologies and methods.
Further, the user can very quickly sort "through
on process stream characteristics and desired
or waste minimization performance criten
can
stream-
hem based
eparation
-------
Who Are the Developers!
The Center for Waste Reductiori Techn
(CWRT)
The M.W. Kellogg Company
The National Center for Clean
Treatment Technologies (Cen
4 The Department of Energy - O
Technologies
4 ENSR Consulting & Engineering
4 The Bechtel Corporation
logies
Industria and
ice of Inustrial
-------
Knowledge ContnbutT
Organizations
4 HazTECH Publishing, Inc.
4 High Tech Resources Internation
4 Chemical Manufacture's Associa
4 Texas Natural Resource Conserv
4 Hydrocarbon Processing Magazine
(Gulf Publishing Company)
4 AlChE & Chemical Engineering Progress Magazine
4 Environmental Protection Agency -WE Program
4 CWRT sponsors and over 450 other organizations
ission
-------
Why Was It Developed?
4
4
No such compendium of information exists today'
Innovative separation technology information is
crucial to economic pollution prevention
4 To improve technology transfer between
industries and within large organizations
To accelerate the consideration of capable
separation technology outside of the industry
sector where it has been primarily deploed
x^vv^^^
5ปm
-------
is Not the Answer
Publications catalogued 1985-95:
5,708 on distillation
23,108 on extraction
52,726 on adsorption
111,520 on membranes
Technology vendor data
Unpublished information (confer
Corporate information
Patent Literature
;nces)
-------
Benefits
Guidance to accomplish source reduction -
design process changes.
Consideration of other companies'
innovative waste reduction exam pit ปs
gas-gas and liquid-liquid separation technologies which
minimize or eliminate end-of-pipe streams
A water reuse knowledge base enables
quicker incorporation of waste and/or
energy reduction into operatio
-------
The Tool's
Mode of Operation in
sign
e or
Used in the conceptual design pha
earlier to provide:
stream by stream flowsheet review for alternative
technology options
information based on separation performance or
function desired
alternate searches based on technology $roup or
licensor or vendor name
quick review of many separation options
separation and recovery of contaminants
end-of-pipe-treatment
or
in lieu of
-------
Technology Performance Inf
Typically Neede
tion
Phase of the contaminant and carrie
(gas, liquid, or solid)
Chemical group of the contaminant
carrier stream
Applicable temperature and
nd
pressure ranges
Applicable flow rate and contaminan^
concentration
Contaminant recovery desired
Commercial status desired
-------
Current Status
Version 1.0 Released J
Version 2.0 under development
ly 1998
-------
CPI
X
Separatio
Tool
onstration
echnol
-------
SCENARIO 1 - PHENOL AND ACETONE PRODUCTION PROCESS
You are the new process engineer at a world-scale phenol and acetone production plant.
You have been asked to investigate the potential options to reduce the contaminant or
pollutant content in the following gaseous process effluent streams:
The Phenol Oxidizer off-gas vent stream,
The Cumene Hydroperoxide (CHP) concentration vent recovery system
effluent,
The Cumene Hydroperoxide (CHP) separator overhead stream, and
The Phenol Oxidation area equipment vents.
You have been told by your supervisor that the only chemicals that you should be
concerned with in these four effluent streams are: Cumene, Cumene Hydroperoxide (CHP),
Phenol, Organic Acids, Aldehydes, Ketones, and heavy aromatics. Consider that all
contaminants are currently below 1,000 ppm and currently are being used as fuel in the
boilers to raise steam for the process operations.
Your objective is to reduce the contaminants in these streams by at least 99% from their
current low levels. You are to compare the in-process options to what would be required at
the end-of-pipe for treatment to meet the upcoming environmental regulations. Once the
best two options are identified, you are to use a process simulator to verify the effects (or
lack thereof) on the rest of the production process.
SCENARIO 2 - PHENOL AND ACETONE PRODUCTION PROCESS
You are the new process engineer at a world-scale phenol and acetone production plant.
You have been asked to investigate the potential options to reduce the contaminant or
pollutant content in the following aqueous process effluent streams:
Recycle from Cumene and AMS The Phenol Oxidizer off-gas vent stream,
The Cumene Hydroperoxide (CHP) concentration vent recovery system
effluent,
The Cumene Hydroperoxide (CHP) separator overhead stream, and
The Phenol Oxidation area equipment vents.
You have been told by your supervisor that the only chemicals that you should be
concerned with in these four effluent streams are: Phenol, methyl hydroperoxide (MHP),
formaldehyde, methanol, formic acid, hydrogen, and heavy aromatics. Consider that all
contaminants are currently below 100 ppm and currently are separated in a multi-stage
stripper unit followed by biotreatment of the water, recovery of the condensable overhead,
and use as fuel for the remaining light ends.
Your objective is to reduce the contaminants in these streams by at least 90% from their
sub-100 ppm levels and suggest alternative pollution prevention options for the existing
separation and treatment systems. Once the best two options are identified, you are to use
Pollution Assessment And Prevention Software For Chemical industry Process Simulators
Pollution Prevention Module Update Page 1 of 2
-------
a process simulator to verify the effects (or lack thereof) on the rest of the production
process.
SCENARIO 3 - METHANOL PRODUCTION PROCESS
You are an experienced process engineer at a world-scale methanol plant. Your
assignment is to identify and evaluate the two best options for increasing plant production.
Because cost is a very important factor, the two options must take into account all of the
current and near-future safety, health, and environmental requirements for methanol
production. The most important gaseous process effluent streams are:
The Synthesis loop purge, and
The Refining column overhead gas.
The most important aqueous process effluent streams are:
The Fusel Oil side draw from the Refining column,
Refining column bottoms, and
Process condensate.
Your best process information indicates that the synthesis loop purge is fairly large and
contains hydrogen, carbon monoxide, carbon dioxide, argon, nitrogen, and some methanol.
The refining column overhead gas contains acetone, methanol, dimethyl ether,
formaldehyde, and methyl formate. These two streams are now fed to the boilers for steam
generation.
In your data gathering for the aqueous effluent streams, you have found the Fusel Oil
stream to contain 36% methanol, 6.3% ethanol, 1.5% i-propanol, 0.6% i-butanol, and 55.3%
water. This stream now goes to the boilers as fuel for generating steam. The refining column
bottoms is almost entirely water with a very low concentration of methanol present and is
currently routed to biological treatment. The process condensate is also mostly water with a
small amount of dissolved gases and some methanol. This stream currently is stripped with
steam and recycled back to the boiler feed water steam system with the stripping steam
recycled to the Reformer inlet.
Once the best two options are identified, you intend to use a process simulator, as always in
design, to verify the effects (or lack thereof) on the rest of the production process.
Pollution Assessment And Prevention Software For Chemical Industry Process Simulators
Pollution Prevention Module Update Pa9e 2 of 2
-------
-------
Comparative Cost Studies
for Presentation to the
VOC Recovery Seminar
Cincinnati. Ohio
September 16-17,1998
Presented by
Edward C. Moretti
Baker Environmental
-------
VOC Abatement Strategies
Prevention
Material substitution
Process optimization
Work practices
Recovery
Adsorption
Absorption/Distillation
Condensation
Membrane Separation
Volume Reduction
Destruction
Thermochemical destruction [thermal oxidation, catalytic oxidation,
flaring)
Photochemical destruction [UV oxidation)
Plasma/Electron beam destruction
Biofiltration
-------
Choosing the Right Reduction Strategy
Characterize Emissions
Type of pollutant
Emission rate
Identify Environmental Objectives
Regulatory-Driven Emissions Control
- Identify applicable VOC regulations
- Identify VOC abatement options that meet regulatory requirements
Waste Minimization-Driven Emissions Control
- Define corporate culture and business objectives
- Identify VOC abatement options that eliminate or reduce waste
sources
-------
Choosing the Right Reduction Strategy
Evaluate VOC abatement options
Applicability
- Exhaust stream flowrate
- Exhaust stream concentration
- VOC categories (ketones, alcohols, halogens, hydrocarbons)
Energy
- Utilities requirements
Environmental
- Secondary environmental impacts
- Opportunities for recycle
- Fugitive emissions
-------
Choosing the Right Reduction Strategy
Economic
- Pretreatment considerations (dilution, preheating, precooling,
humidification, dehumidification, paniculate removal, entrained
liquid removal)
- Maintenance requirements
- Capital Costs
- Annualized Costs
Select most cost-effective option meeting environmental
objectives
-------
VOC Abatement Options - Applicability
ecnnology
Gas Concentration
Gas Rowrate
Low
(<500 ppmv)
High
(>500 ppmv)
Low
(<1,000scfm)
Medium
(1,000-10,000 scfm)
High
000 scfm)
Adsorption
Absorption
Condensation
Membrane
Separation
Volume
Destruction
Catalytic
Oxidation
Photochemical
Destruction
Plasma/Electron
Beam Destruction
Biofiltration
-------
VOC Abatement Options - Costs
Variable based on customer specifications
Industrial- $$$
Commercial- $$
Municipal - $
Variable based on:
Site preparation costs
Instrumentation and controls
Energy costs (fuel, electricity]
Solvent recovery value
Operating/maintenance costs
VOC concentration
Exhaust stream flowrate
Number of VOCs in exhaust stream
Type of VOC
-------
Cost Estimation Techniques
Best engineering judgement
Published guidance
Vendor assistance
-------
Published Cost Guidance
USEPA CO$T-AIR
USEPA HAP-PRO
USEPA OAQPS Cost Manual
USEPA Background Information Documents
Technical Associations
State/Local Agency Guidance
-------
Comparative Costs
Based on industrial experience
Trends are consistent with USEPA cost programs
NonhalogenVOCsinair
Natural gas = $2.10/MMbtu
Electricity = $0.04/kWh
Water = $0.08/10,000 gallons
Catalyst life =5 years
Wastewater treatment=$0.50/lb VOC
Value of recovered solvent=$0.50/lb VOC
Membrane life=3 years
-------
Comparative Capital Costs
VOC = 100ppmv
en
**
ฃUUU
1750 -
1500 -
1250 -
1000 -
750 -
500 -
250-
0-
*
i
l
1
-i- -
i
i
j
X's^
\
\ v- \
? \, \
"* -v \ X._. j_ _ _ j-rf-j-^ ha^-n.-B.-. r
^^-^Ijtrrrr c~ " o-^- :.~ - --. ^ -^ '
10000 20000 30000 40000 50000 60000 70000 80000 90000 100000
Exhaust Gas Flowrate (scfm)
-* Catalytic Oxidation
A Regenerative Adsorption
*- Condensation
+----Volume Reduction
D Regenerative Thermal Oxidation
x Absorption
Membranes
-------
60
50
40
jo 30
20
10
Comparative Annualized Costs
VOC = 100ppmv
70
10000 20000 30000 40000 50000 60000 70000 80000 90000 100000
Exhaust Gas Flowrate (scfm)
Catalytic Oxidation ฐ Regenerative Thermal Oxidation
Regenerative Adsorption x Absorption
Condensation
-------
Additional Thoughts
Consider the Waste Minimization approach to VOC
abatement
Strong public support for environmental protection
Stockholder pressures on industry to demonstrate responsible care
Sustainable development/green design ualues are strongly held, widely
shared
Expect pollution prevention to prevail
Innovative technologies that combine pollution abatement with
manufacturing process improvements have higher likelihood of
commercial success
According to U.S. Commerce Department, corporate spending on so-
called "integrated technologies" has more than doubled since 1983
-------
-------
Availability of Technology Information,
Including Internet-Based Sources
rto Cabezas, Ph.D.
Protection Agency
Risk Management Research Laboratory
Sustainable Technology Division
II Pill^artin Luther King Drive
Cincinnati, Ohio 45268
-------
Topics of Discussion
Solvent Alternatives Guide
Computer Aided Molecular Design
II: Program for Assisting the
Replacement of Industrial Solvents
PIP: Pollution Prevention Progress
WAR: Waste Reduction Algorithm
-------
SAGE: Solvents Alternatives Guide
Developers: Surface Cleaning
Program at Research Triangle Institute
in cooperation with the U.S. EPA Air
Pollution Prevention and Control
livision (APPCD).
http://clean.rti.org/
-------
SAGE: How it does work?
SAGE works as both an expert system that will evaluate
various process and chemistry alternatives for a particular
situation and as a hypertext manual on cleaning
alternatives.
The expert system or advisory portion of SAGE will ask a
series of questions about the particular part(s) that you are
trying to clean. These are the same questions that a
process engineer would have to answer when changing
processes e.g. questions on size, part volume, nature of
the soil to be removed, production rate, etc.
-------
SAGE: How does it work?
Once the question and answer session is complete, the
system will return a listing of the processes and
chemistries, together with a relative score, most likely to
particular situation. The relative score will
the alternatives.
Each alternative listed will also be a hyperlink to further
i||i||ii||||i||n the general use of the process or chemistry,
safety data, and case studies.
The Solvent and Process Alternatives Index can be used to
directly access information on the various alternatives
listed in SAGE. This method is best used when you only
want to retrieve a copy of the information available for a
certain alternative. This method will not provide any
ranking information based on your process requirements.
-------
CAMD: Computer Aided
Molecular Design
Rafiqul Gani & Peter Harper
Computer Aided Process Engineering Centre
Department of Chemical Engineering
Technical University of Denmark
DK-2800 Lynghy
Denmark
-------
CAMD: Methodology
methodology is of the "Generate and
unds of the desired type are generated.
compounds are screened against the
Needed tools are:
Structure generation algorithm
Property prediction methods
Selection/Search algorithms
-------
CAMD: Application Steps
1: Problem formulation (solute properties,
target properties, knowledge-base)
HlllliPeneration/testing of fragments
(groups description, estimate primary properties)
Step 3: Generation/testing of final structures
(generate isomers, estimate primary, secondary, functional
properties)
Step 4: Generate Atomic description &
Search data-base (atomic description of candidates)
Step 5: Final selection & analysis (sort
candidates for a specified properties, structural properties)
-------
PARIS II: Program for Assisting the
Replacement of Industrial Solvents
Cabezas, R. Zhao, and J. C. Bare
|p>. Environmental Protection Agency
National Risk Management Research Laboratory
26 West Martin Luther King Drive
Cincinnati, Ohio 45268
&
S. R. Nishtala
Research Triangle Institute
3040 Conrwallis Road
Research Triangle Park, North Carolina 27709-2194
-------
PARIS II: Description
Second generation solvent design software
a chemical or designs a chemical
mixture that match desired solvent
Uses the static, dynamic, performance, and
environmental solvent properties
Yields application independent substitute
solvents
-------
PARIS II: Properties
Static: molecular mass, density, boiling
|[|||nt, vapor pressure, activity coefficients
Ill^mic: viscosity, thermal conductivity
il||ormance: flash point
Environmental: air index, total
environmental index
Demo:
www.rti.org/units/ese/p2/PARIS1.html
-------
P2P: Pollution Prevention
Progress
||reg Carroll, David Pennington1, Robert
Knodel2, David Stephan3
Environmental Protection Agency
National Risk Management Research Laboratory
26 West Martin Luther King Drive
Cincinnati, Ohio 45268
1 Post-doctoral Research Associate, ORISE
2 Senior Environmental Employee (SEE) Program Associate
3 Retired, 2/96
-------
P2P: Description
r-friendly, computer-based tool for assessing pollution
(or sometimes increased) as a result of product
reformulation, or replacement;
February 1995; Mark II released July 1997.
InBnHHAiafter snapshots and reports describing P2
|:|:!OWI^ * B *^
with respect to media (water; soil/ground water;
of pollution (human health; environmental use
lililj^ capacity; and life-cycle stages)
1 li|||i|i||||n for 22 classes of pollution prevented (toxic
organics; toxic inorganics; carcinogens, teratogens,
mutagens; fine fibers; heavy metals; radioactives; pathogens;
acid rain precursors; aquatic life toxics; global warmers;
BOD; COD; nutrients; dissolved solids; corrosives; ozone
depleters; particulates; smog formers; suspended solids;
odorants; solid wastes; hazard wastes)
Accounts for energy-related pollution associated with P2.
-------
P2P: Releases
BgP - MARK II
the following improvements over Mark I:
+ Database of almost 3000 pollutants
: :_^v:;-.x >:.;ro.::::-.-::'-:-.-:- '-.':::'::- :>:;.::;-;:;X;?::; -:-;. ;':> :>.;":>":-. I
search by CAS No. and synonym
deal with incompletely-classified pollutants
report potential regulatory impact
Development underway; improvements over Mark II:
Windows-based program
Accounts for "potencies" of pollutants (i.e.,
characterization) with respect to environmental and
health impacts
Restructuring of impact categories to improve
comprehensiveness, consistency with other SAB tools
-------
WAR: Waste Reduction
Algorithm
D. Young, H. Cabezas,, and J. C. Bare
U.S. Environmental Protection Agency
National Risk Management Research Laboratory
26 West Martin Luther King Drive
Cincinnati, Ohio 45268
&
G. Pearson
Chemstations, Inc.
2901 Wilcrest Drive, Suite 305
Houston, Texas 77042
-------
-------
O
xapuj
10
-------
SUMMARY
software for finding or designing
solvent substitutes
One software for quantifying pollution
prevention progress
One software for using design to reduce
pollution in chemical processes
-------
VENT
By
Charles H, Darvin
U.S. Environmental Protection Agency
National Risk Management Research Laboratory
Research Triangle Park, NC 27711
-------
FLOW MANAGEMENT
AND REDUCTQN
BACKGROUND DISCUSSION
Technical Feasibility vs
Economic Feasibility
OVERVIEW
- Background; Air Flow Management
- Spray Booth Recirculation
- Recirculation Issues
- Booth Design Concept
- Results of Booth Development
and Demonstration
- Summary
BACKGROUND DISCUSSION
Process Air
- Support reaction
- Provide a safe painting
or surface cleanini
environment
-------
BACKGROUND DISCUSSION
Air Flow
Reduction Techniques
- Reduce direct air input
- Air recirculation
WHY CONSIDER RECIRCULATIQN
IN SPRAY BOOTHS?
4 Reduced Control Ikjuipment Cost
4 Reduced Operating Cost
+ Allow for Continued Use of Existing
High Solvent (VOC) Coatings
4 Acceptable as an Emissions Control
Alternative
AIR RECIRCULATION
IN PAINT SPRAY
BOOTHS
SPRAY BOOTH RESEARCH
Problem: Treatment of
Spray Booth Discharge Emissions
# Capital Cost ($) = f ((tow)
* Operating Cost ($) = (flow)
* No Economical Control Options
Goal: Reduce Exhaust Howrate
to Air Pollution Control System
-------
WHAT IS
RECIRCULATION?
EXHAUST RECIRCULATION
SPRAY BOOTH VENTILATION
CONVENTIONAL
SPRAY BOOTH EXHAUST
INTERPRETING GOVERNMENT
AGENCY REGULATIONS
of
-------
RECIRCULATION ISSUES
Does recirculation violate the
intent of OSHA regulation:
1910,94 and (910.107?
Does recirculation, as
recommended and presently used,
present an added safety burden?
OSHA 1910,107
Spray Painting Using Flammable
and Combustible Materials
Interpreted to Forbid
Recirculation
OSHA 1910.94
VENTILATION (C) (3):
Design and construction
of spray booths
OSHA 1910,1000
-------
EQUIVALENT TOXICITY
OF RECIRCULATED STREAM
L
[concentration],
TWA,
Where:
[concentration], = Conoentraiion of each
hazardous constituent
TWA, = TWA (rime Weighted Average)
of each hazardous constituent
SCHEMATIC DIAGRAM OF A
SPLIT-FLOW VENTILATION SYSTEM
%
VERTICAL DISTRIBUTION OF
^ EXHAUST
2 4 6 8 10 12 14
HEIGHT ABOVE FLOOR (It)
TOTAL ORGANICS
METALS
ISOCYANATES
PARTICIPATES
SPRAY BOOTH DESIGN
-------
'-:'
'-;";'
1
ฃฃfeW^%S'3:^:" ' ''.i; "; 3!i -.V '. V
li
PROJECTED CONCENTRATIONS
Initial Kate: 55,000 cfm
Pul lull lit
\I1\WIM
Butyl A n: UK-
Xylciio
Naphthalene
Dtclhyl-
[ililhalalc
Di-n-liulyt-
plllhllali;
ฃ GTWA
Exluusi rjio,
tint
OSIIA
mmg/m'
719 nij./nป'
4 ป ing/in'
SO in^/iii'
S ing/ in1
S nig/in'
Dctcclctl
CoiiiYnlrittim
S.S iiiji/in'
4.V ,nj./m'
-
O.OOS ins/,i>-
(1.1)27
Si.IKHl
25%
6.9
6.1
0.2S7
ll.OOfi
0.017
0.1)10
fl.OJ
1 1 .(MX)
7S%
9.6
11.]
IU60
o.ms
0.02 S
O.OH
O.OS
1 1.750
90%
16.)
14. S
O.J'H
D.Oll'J
M.OJ6
0.0 IS
. 0. 1 1'J
S.'ilHt
PAINT BOOTH RECIRCULATION
S ( - ' ' ' '
j
COST SAVINGS
USING RECIRCULATION
Pro - Mod
Uooth
ExIiauM
in1/ inin
(Clill)
1SS6
(S 5,000)
POM - Mod
lioolh
I:xl].nts!
in1/ mill
(dm)
S72
(20,210)
IVt- - Mod
EsiimaU'd
COM
(S x 10')
I.I
Pซst - Mod
Estimated
Cosi
(S x 10'-)
0.4
Pro - Mod
Operating
Cost
(S x 10')
13.0
Post - Mod
Operating
Cost
(S x 10')
SO
WHY IT WORKS
* Pollutants, typically, are heavier than air
* Heavier solid and gaseous pollutants fall to
lower levels of booth prior to exhaust
* Pollutants follow flow streamlines from release
point or fall to booth floor
* Recirculated air is relatively clean of paint
pollutants
* Kecirculated concentration does not approach
health and safety limits
* Health and safety limits are based on
concentration, not total volume, of pa ait used
-------
-------
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itilSPi^^
ij^i^^
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-------
-------
VOC Recovery Seminar
Questionnaire
Trends/Issues/Research Needs By Industry
Break-out Session, Thursday, September 17
Contact Information (Optional)
Name:
Title:
Organization and Mailing Address:
Telephone:
Email:
Fax:
-------
VOC Recovery Seminar
Questionnaire (Continued)
Trends/Issues/Research Needs By Industry
Break-out Session, Thursday, September 17
(If possible, we recommend that each seminar attendee complete this questionnaire in
advance of the seminar and bring the results to the seminar.)
To Be Answered By Consultants, Government Employees. University Representatives,
NGOs
1) What types of organic (volatile or non-volatile) destruction and recovery technologies and
applications have you evaluated/permitted during the course of your work?
2) What are the relative differences in capital, operating, and maintenance costs between
destruction and recovery systems that you have encountered (if known)?
3) Are there potential cost differences if one uses a life cycle assessment view (i.e., cradle to grave
considerations of materials consumed and byproducts/wastes generated)?
4) Can you identify the barriers for switching from a destruction to a recovery process?
-------
VOC Recovery Seminar
Questionnaire (Continued)
Trends/Issues/Research Needs By Industry
Break-out Session, Thursday, September 17
5) Do you have suggestions as to how to minimize or eliminate these barriers?
6) Are there any special problems inherent in the destructive processes that are overlooked
because they are "known or established technologies"?
7) What issues/problems have you encountered with the recycle/ reuse of organics?
-------
VOC Recovery Seminar
Questionnaire (Continued)
Trends/Issues/Research Needs By Industry
Break-out Session, Thursday, September 17
To Be Answered By Industry Representatives and Manufacturers/Pesigners/Pistributors of
Technologies
1) Do you have any organic (volatile or nonvolatile) streams presently treated by destruction that
might be candidates for recovery (if uncertain, assume they may have a potential for
recoverability)?
a) If so, describe each of these streams.
b) What are the chemical constituents in each of these organic streams (if possible,
include % volume or weight of each chemical)?
c) What are the organic concentrations in these streams, and what are the stream
flowrates?
-------
VOC Recovery Seminar
Questionnaire (Continued)
Trends/Issues/Research Needs By Industry
Break-out Session, Thursday, September 17
2) What types of destruction processes do you use to treat your organic streams?
3) What are the approximate capital, operating, and maintenance costs for these processes?
4) Are there potential cost differences if one uses a life cycle assessment view (i.e., cradle to grave
considerations of materials consumed and byproducts/wastes generated)?
5) Can you identify the barriers for switching to a recovery process?
-------
VOC Recovery Seminar
Questionnaire (Continued)
Trends/Issues/Research Needs By Industry
Break-out Session, Thursday, September 17
6) Do you have suggestions as to how to minimize or eliminate these barriers?
7) Who is the individual or what is the corporate function in your organization that is key in
getting recovery processes evaluated to replace destructive processes?
8) Have you evaluated any recovery process, and, if so, what have been your experiences?
9) Are there any special problems inherent in the destructive processes that are overlooked
because they are "known or established technologies"?
-------
i
VOC Recovery Seminar
Questionnaire (Continued)
Trends/Issues/Research Needs By Industry
* Break-out Session, Thursday, September 17
I 10) What issues/problems have you encountered with the recycle/ reuse of organics?
i
i
To Be Answered By All Seminar Participants
1) What organic recovery research programs do you think should be undertaken and why?
i
2) What modifications/additions to existing research programs do you think are needed and why?
3) What types of economic/compliance incentive programs are needed to encourage the use of
innovative organic recovery technologies?
-------
VOC Recovery Seminar
Questionnaire (Continued)
Trends/Issues/Research Needs By Industry
Break-out Session, Thursday, September 17
4) What improvements in recovery technologies are needed to increase the use of these
technologies (in your facility, with your stakeholders, in industry as a whole)?
5) What sources of information (e.g., how-to manuals, guidance documents, technology
handbooks, etc.) do you think are needed to improve the general understanding of organic
recovery technologies as well as to encourage their use?
-------
-------
-------
U.S. EPA VOC Recovery
Seminar Follow-On Efforts
Scott R. Hedges
EPA Seminar Manager
Technology Transfer and Support Division
National Risk Management Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, Ohio
-------
Summary and Concluding Remarks
- VOC Recovery Seminar
There is a need for more guidance
documents and information on source
reduction - process design and VOC
VOC recovery technologies
Need to incorporate pollution
prevention/waste minimization into VOC
recovery/source reduction decisions
-------
Summary and Concluding Remarks
- VOC Recovery Seminar cont.
Need to improve recovery cost-
effectiveness in part through flow VOC
concentration and flow reduction
Need to continue to convert
promising/emerging recovery technologies
into viable commercial applications
-------
Summary and Concluding Remarks
- VOC Recovery Seminar
There is a need for more guidance
documents and information on source
reduction - process design and VOC
VOC recovery technologies
Need to incorporate pollution
prevention/waste minimization into VOC
recovery/source reduction decisions
-------
Summary and Concluding Remarks
- VOC Recovery Seminar cont.
Need to improve recovery cost-
effectiveness in part through flow VOC
concentration and flow reduction
Need to continue to convert
promising/emerging recovery technologies
into viable commercial applications
-------
Follow-on Efforts and Documents
- VOC Recovery Seminar
Seminar Presentation Materials to be
summarized and provided in a
proceedings report.
Results of Break-out Sessions on VOC
Recovery Research/Information Needs - to
be compiled and presented in the seminar
proceedings report.
-------
Follow-on Efforts and Documents
- VOC Recovery Seminar cont
Videotape of Seminar Presentations to be
edited and distributed as a technology transfer
aid through USEPA's Center for Environmental
Research Information (CERI).
Possible development of an interactive CD
ROM highlighting the seminar presentations
with linkages to important sources of
information both within and external to USEPA.
-------
Follow-on Efforts and Documents
- VOC Recovery Seminar cont.
Preparation of a Handbook on VOC
Recovery Technologies - Handbook will
describe the technical feasibility and cost-
effectiveness of current and emerging
recovery technologies as well as guidance
on recovery technique selection.
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