VOC Overview

• Program Description:
– Custom-designed and built integrated VOC control systems
with turnkey installation at a competitive price by combining the
engineering and design expertise of Polaris, with the project
management, system integration and gas supply of Praxair.
• Value Proposition:
– Praxair will offer systems for controlling VOC emissions at the
lowest price by bringing equipment to market from small,
specialized suppliers. Praxair’s VOC control offering will
provide the lowest cost system to achieve emissions control
requirements. When appropriate, VOCs will be safely and
economically recovered for reuse.
• Status: Commercialization
 VOC Market Opportunity
• The VOC control market is large:
– $767 million market in 2002
– VOCs are a pollutant of focus now due to its contribution to ground-level
ozone (along with NOx)
• Prospects are strategic markets for Praxair:
APC Equipment Market, 2001
– Chemicals Total Market = $3.78 billion

– Refineries
– Pharmaceuticals Fabric Filters:
Precipitators:
24%
• Driver is regulations 13%

– CAA MACT standards

Desulfurization:
– SIP (Texas) 13%

– Enforcement

VOC/
Oxidation: 20% NOx Control:
Other: 8% 21%
Carbon: 3%
Source: Environmental Business
International (San Diego, CA)
 VOC Business Model
• Sales Process • Capital & Revenue
• Get the survey call results to
Polaris for an initial review
Examples
• • BP Solvay (Deer Park, TX):
Set up a teleconference with
– Equipment capital $ 1,011,000
Prospect & Polaris
– Equipment revenue $ 360,000/year (or
• Receive Polaris’ proposal: $1,100,000 SOE)
– preliminary process design &
– Equipment ROC (IRR) >20%
explanation
– equipment pricing – LN2 demand: 48,000 cfh max.
– LN2 & utilities estimates – LN2 revenue (@$0.30/ccf) $121/hr for 250
hr/mo = $435,000/year
• Decide on the annuity or SOE
– Value of recovered VOC $500/hr
(or both) and pricing
• Make the appropriate changes – Total revenue $ 795,000/year
to the Polaris proposal and
present it
VOC Market Space
VOC Mkt

Regulated Economic Motivation

Cost Fluctuates Cost Constant

Immediate Expected

Indifferent
Indifferent
VOC
Consent Decree Green Customer Green Customer

NESHAP MACT Texas SIP

Harris C2, C3, C4 HGA C2, C3

Market Opportunity Assessment
• Technologies are well developed:
– Oxidation (RTO, catalytic)
– Condensation
– Adsorption
– Membrane
• The APC market is served by hundreds of firms:
– 75% of revenues go to firms <$100 MM/year
– The largest VOC equipment supplier is <$65 MM/year
• Each system must be designed for the requirements of
the customer’s site:
– Low-cost engineering is a competitive advantage
– No inventory required
VOC Drivers
• Volatile Organic Compounds
– Regulated because they react to form ground level ozone
under certain conditions.
– Regulated in conjunction with NOx
• VOC market initially targeted capturing the compound and
incinerating it in oxidation process
– Relatively simple design
– Trading VOC for NOx source
– No economic benefit of recovery
• VOC market today giving customers choice of collection for
disposal, or reuse
– More complex systems
– Eliminates NOx problem
– Gain economic value from reused raw material
 Principle of Cryocondensation
Cleaned
Vent Gas TIC

LIN

VGC Unit
Temperature

Vent GN2
Gas

Vapor Pressure
Condensate
Cryogenic Condensation

Feed Gas inlet

LN2 in
Regeneration
system

Light gases
Precooler

for vent or
recovery

High purity
GAN out

Key factors:
•Flow
•Concentrations (in & out) Collector
•Volatility of components
•Temperature of condensation Pump
•Freezing points of compounds
VOC out
Praxair’s VOC Partner: Polaris

• Praxair’s VOC control partner in Europe since 1998.

• An employee-owned engineering company established
in 1996 by experts from the pharmaceutical and
industrial gases industries
• Focused on designing and supplying plants for the
chemical, petrochemical and pharmaceutical industries
• Couples the responsiveness of a small company to the
project execution resources and management capability
of Praxair.
• More than 50 systems installed.
• The Polaris Quality System complies with ISO 9001:2000
Heat Exchanger
Cryogenic Condensation
Cleaned
Vent Gas TIC

LIN
VGC Unit

Vent GN2
Gas

Condensate
 Adsorption
Key factors:
•Adsorptivity of compounds
VOCs more strongly adsorbed than N2, •Required pressures
removed through Depressurization/Heating •Impurities
VOC - Light Gas
Light Gas

Compress
Adsorption
-Drying Beds

Capture or Destruction
Is possible Steam or
Hot Gas

Cooling Drier
Adsorption can achieve low Condenser Decant
residual VOCs without
low temperatures
VOC
Adsorption
Internal Reflux Distillation
 Good Candidates for
Cryocondensation

• Olefin monomers • Solvents with BP > +100 F

– Ethylene, Propylene, Butene, and with FP < -100F (easy to
Butadiene do)
– HRVOC & high value
– Acetone, MEK
• Chlorinated VOCs
– Methylene chloride
– Methylene chloride
– Ethyl dichloride
– Ethyl dichloride
–
– Hexene, Hexane
Vinyl chloride monomer
– Toxic, corrosive – Methanol
– Not good for oxidation – Vinyl/Ethyl Acetates
• Water-soluble compounds – Trichloroethene
– Ethanol, ethyl acetate, acetone, – Toluene, Ethylbenzene
ammonia
– Adsorption/steam regen causes
water pollution
• High value compounds
Polaris Targets for Cryo Solution
In general, Polaris targets applications where compounds are difficult to
handle, the hierarchy may look something like:
I. All Chlorinated Compounds
– More volatile, toxic , carcinogenic, & corrosive
– Can’t burn
– Separation is difficult
– e.g Methyl chloride, vinyl chloride
II. Compounds hard to separate from water
– Solvents soluble in water
– Steam regeneration creates polluted water stream
– requires further treat
– e.g. Ethanol, ethyl acetate, acetone
III. Valuable compounds
IV. Customers with no water treatment available
V. Volatile compounds
– Boiling points<0º
 Economics: $0.40 per 1000 pounds of Feed
$30
NPV (VOC – LN2/Equip)
NPV (VOC+THRMOX – LN2/Equip)
$25

$20 Cryogenic Condensation Preferred

VOC Value $/hr

$15

$10 Thermal Oxidation Preferred

$5

$0
0 10000 20000 30000 40000 50000 60000 70000

Total Mass Rate, lb/hr

Figure 3 – LN2 Based Breakpoint Curve for Economic Justification

Praxair/Polaris Installations
CUSTOMER TYPE COUNTRY FLOWRATE MAIN COMPOUNDS
IPIRANGA CHEM BRASIL 2600 HEXANE
CIRES CHEM PORTUGAL 120 VINYL CHLORIDE
WITCO CHEM SPAIN 350 METHYL CHLORIDE
DIASPA PHARM ITALY 1000 METHYLENE CHLORIDE, METHA
SEALT CHEM ITALY 30 SOLVENT MIX
BAYER PHARM SPAIN 50 KETONES
DAC CHEM ITALY 200 ETHYLENE OXIDE
EURAND CHEM ITALY 6000 CYCLOHEXANE
ENICHEM RAVENNA CHEM ITALY 200 ACRYLONITRILE
INDINOR CHEM PORTUGAL 20 METHYL ACRYLATE
 Specific Discussions
• Feed gas • Cleaned gas
– Average flow (nm3/h) – Temperature & Pressure
– Peak (flow, duration, & – Residual VOC expected
frequency) – Desired use (GAN for
– hrs/day, days/week purge?)
– Temperature & Pressure • Recovered VOC stream(s)
• Feed composition – State (gas, liquid)
– Air, N2, H2O – Residual N2 expected
– Key VOC’s – Purity expected (VOC
– Trace contaminants content)
– Other light gases (H2, – Desired use (recycle, fuel)
CH4?) • Constraints
• Nitrogen needs – Required VOC reductions
– Flow, T & P, purity – NOx limitations on flares
– Source (tank, pipeline)
Row #
Target Chemicals
HAP CRYO Chemical Fugitive Air Stack Air Total Air Emissions % Total Stack Air Cum %
1 Yes yes METHANOL 35,518,718 140,325,888 175,844,606 20.300% 20.300%
4 Yes yes TOLUENE 26,855,385 44,684,319 71,539,704 6.464% 26.764%
7 Yes yes N-HEXANE 16,290,521 31,353,824 47,644,345 4.536% 31.300%
10 Yes yes METHYL ETHYL KETONE 11,503,653 17,591,289 29,094,942 2.545% 33.844%
11 Yes yes CARBON DISULFIDE 1,577,890 16,579,399 18,157,289 2.398% 36.243%
13 Yes yes DICHLOROMETHANE 6,809,500 14,747,847 21,557,347 2.133% 38.376%
18 Yes yes METHYL ISOBUTYL KETONE 2,168,330 7,864,785 10,033,115 1.138% 39.514%
22 Yes yes ETHYLBENZENE 1,754,673 4,792,702 6,547,375 0.693% 40.207%
28 Yes yes TRICHLOROETHYLENE 4,899,521 3,349,796 8,249,317 0.485% 40.692%
30 Yes yes METHYL TERT-BUTYL ETHER 1,005,042 2,284,045 3,289,087 0.330% 41.022%
32 Yes yes VINYL ACETATE 791,477 2,083,158 2,874,635 0.301% 41.324%
39 Yes yes TRIETHYLAMINE 450,286 1,174,030 1,624,316 0.170% 41.494%
45 Yes yes CHLOROPRENE 43,635 808,374 852,009 0.117% 41.610%
46 Yes yes CUMENE 505,088 754,632 1,259,720 0.109% 41.720%
50 Yes yes ACRYLONITRILE 324,985 610,869 935,855 0.088% 41.808%
63 Yes yes PROPIONALDEHYDE 53,068 337,569 390,637 0.049% 41.857%
71 Yes yes ACROLEIN 4,815 246,408 251,223 0.036% 41.893%
95 Yes yes 1,2-DICHLOROPROPANE 74,268 86,747 161,015 0.013% 41.905%
108 Yes yes ETHYL ACRYLATE 48,482 56,000 104,482 0.008% 41.913%
126 Yes yes ALLYL CHLORIDE 9,441 25,709 35,150 0.004% 41.917%
146 Yes yes 2-NITROPROPANE 8,217 9,066 17,283 0.001% 41.918%
174 Yes yes 1,2-BUTYLENE OXIDE 2,117 4,022 6,139 0.001% 41.919%
15 yes N-BUTYL ALCOHOL 3,699,980 13,151,722 16,851,702 1.903% 43.821%
24 yes 1,1-DICHLORO-1-FLUOROETHANE 2,958,969 4,451,303 7,410,272 0.644% 44.465%
48 yes 2-METHOXYETHANOL 117,646 738,496 856,142 0.107% 44.572%
52 yes SEC-BUTYL ALCOHOL 228,508 558,970 787,478 0.081% 44.653%
67 yes BUTYRALDEHYDE 151,266 288,531 439,797 0.042% 44.695%
83 yes METHYL ACRYLATE 78,316 162,983 241,299 0.024% 44.718%
100 yes 2-ETHOXYETHANOL 21,525 81,944 103,469 0.012% 44.730%
139 yes ALLYL ALCOHOL 110,018 15,440 125,458 0.002% 44.732%
144 yes ISOPROPYL ALCOHOL(MANUFACTURING,STRONG-ACID
12,198 PROCESS
9,783 ONLY,NO SUPPLIER)
21,981 0.001% 44.734%
149 yes 3-CHLORO-2-METHYL-1-PROPENE 70 7,847 7,917 0.001% 44.735%
164 yes CROTONALDEHYDE 7,616 5,146 12,762 0.001% 44.736%
184 yes 1,2-DICHLOROETHYLENE 2,642 2,460 5,102 0.000% 44.736%
219 yes ALLYLAMINE 251 863 1,114 0.000% 44.736%
265 yes ETHYL CHLOROFORMATE 5,251 262 5,513 0.000% 44.736%
118,093,368 309,246,228 427,339,596
Other Questions

• 1) Acceptable presence of water in VOC

• 2) Acceptable presence of VOC in water
• 3) Field of activity of the customer (this helps us in
understanding the scenario in terms of expected
quality level, the operation expertise, etc.)
• 4) What facilities are already available (i.e. steam,
water treatment systems, etc.)
• 5) What alternative they are studying and what is
the expected cost (at least some impression is
appreciated)