INCORPORATING PRODUCT DESIGN INTO THE …...PRESENTATION OUTLINE 1. Background 2. The Use of...
Transcript of INCORPORATING PRODUCT DESIGN INTO THE …...PRESENTATION OUTLINE 1. Background 2. The Use of...
INCORPORATING PRODUCT DESIGN INTO INCORPORATING PRODUCT DESIGN INTO INCORPORATING PRODUCT DESIGN INTO INCORPORATING PRODUCT DESIGN INTO INCORPORATING PRODUCT DESIGN INTO INCORPORATING PRODUCT DESIGN INTO INCORPORATING PRODUCT DESIGN INTO INCORPORATING PRODUCT DESIGN INTO
THE DEVELOPMENT OF NEW THE DEVELOPMENT OF NEW THE DEVELOPMENT OF NEW THE DEVELOPMENT OF NEW THE DEVELOPMENT OF NEW THE DEVELOPMENT OF NEW THE DEVELOPMENT OF NEW THE DEVELOPMENT OF NEW
REFRIGERANTSREFRIGERANTSREFRIGERANTSREFRIGERANTSREFRIGERANTSREFRIGERANTSREFRIGERANTSREFRIGERANTS
By: Isaac Anderson and Christopher DiGiulioBy: Isaac Anderson and Christopher DiGiulio
[1] Vapor-Compression Refrigeration. Answers.com. 4/27/2007 <http://www.answers.com/topic/vapor-compression-refrigeration>.
PRESENTATION OUTLINEPRESENTATION OUTLINEPRESENTATION OUTLINEPRESENTATION OUTLINEPRESENTATION OUTLINEPRESENTATION OUTLINEPRESENTATION OUTLINEPRESENTATION OUTLINE
1.1. BackgroundBackground2.2. The Use of Consumer Preference Functions The Use of Consumer Preference Functions in Refrigerant Designin Refrigerant Design
3.3. Design of New Refrigerants Based on Design of New Refrigerants Based on Consumer Preference Functions and the Consumer Preference Functions and the Chosen MarketChosen MarketA.A. Discussion of Group Contribution TheoryDiscussion of Group Contribution TheoryB.B. Enumeration Modeling in Excel using Group Enumeration Modeling in Excel using Group Contribution TheoryContribution Theory
4.4. ConclusionsConclusions5.5. RecommendationsRecommendations
BACKGROUNDBACKGROUNDBACKGROUNDBACKGROUNDBACKGROUNDBACKGROUNDBACKGROUNDBACKGROUND
HISTORY OF REFRIGERATIONHISTORY OF REFRIGERATIONHISTORY OF REFRIGERATIONHISTORY OF REFRIGERATIONHISTORY OF REFRIGERATIONHISTORY OF REFRIGERATIONHISTORY OF REFRIGERATIONHISTORY OF REFRIGERATION
•• Refrigeration goes back Refrigeration goes back to ancient timesto ancient times
–– Stored Ice Stored Ice
–– Evaporative Evaporative ProcessesProcesses
•• In 1805, Oliver Evans In 1805, Oliver Evans proposed the use of a proposed the use of a volatile fluid in a closed volatile fluid in a closed cycle to freeze water into cycle to freeze water into iceice
HISTORY OF HISTORY OF HISTORY OF HISTORY OF HISTORY OF HISTORY OF HISTORY OF HISTORY OF
REFRIGERATIONREFRIGERATIONREFRIGERATIONREFRIGERATIONREFRIGERATIONREFRIGERATIONREFRIGERATIONREFRIGERATION•• EvanEvan’’s theories most likely s theories most likely influenced Jacob Perkins influenced Jacob Perkins and Richard Trevithickand Richard Trevithick
•• They proposed an airThey proposed an air--cycle cycle system in 1828, but it wasnsystem in 1828, but it wasn’’t t built eitherbuilt either
•• Actual refrigerants were Actual refrigerants were introduced in the 1830s introduced in the 1830s with the invention of the with the invention of the vapor compression system vapor compression system by Perkinsby Perkins
[2] Calm, James M. and David A. Didion. "Trade-Offs in Refrigerant Selections: Past, Present and Future." Int. J. Refrig., 21, 308 (1998).
HISTORY OF HISTORY OF HISTORY OF HISTORY OF HISTORY OF HISTORY OF HISTORY OF HISTORY OF
REFRIGERATIONREFRIGERATIONREFRIGERATIONREFRIGERATIONREFRIGERATIONREFRIGERATIONREFRIGERATIONREFRIGERATION
•• In 1928, Midgely, Henne, and McNary of GM In 1928, Midgely, Henne, and McNary of GM pioneered work to obtain molecules with pioneered work to obtain molecules with desirable properties using systematic designdesirable properties using systematic design
–– They synthesized all 15 combinations of They synthesized all 15 combinations of one carbon with various combinations of one carbon with various combinations of chlorine, fluorine, and hydrogen. chlorine, fluorine, and hydrogen.
–– They finally chose They finally chose dichlorodifluoromethane (Freon) as dichlorodifluoromethane (Freon) as having the most desirable characteristics, having the most desirable characteristics, thus introducing the first thus introducing the first chlorofluorocarbons chlorofluorocarbons
REFRIGERANTS FROM 1830REFRIGERANTS FROM 1830REFRIGERANTS FROM 1830REFRIGERANTS FROM 1830REFRIGERANTS FROM 1830REFRIGERANTS FROM 1830REFRIGERANTS FROM 1830REFRIGERANTS FROM 1830--------
PRESENTPRESENTPRESENTPRESENTPRESENTPRESENTPRESENTPRESENT
•• First GenerationFirst Generation
–– Generally solvents, fuels Generally solvents, fuels or volatile components or volatile components (whatever worked)(whatever worked)
•• Second GenerationSecond Generation
–– CFCs were introducedCFCs were introduced
•• Third GenerationThird Generation
–– Shift to HCFCsShift to HCFCs
•• Fourth GenerationFourth Generation
–– Focused on refrigerants Focused on refrigerants that do no contribute to that do no contribute to global warmingglobal warming
[3] Calm, James M. and Glenn C. Hourahan. Refrigerant Data Update. January 2007. Heating/Piping/Air Conditioning Engineering. Feb. 7, 2007 <http://www.hpac.com/Issue/Article/44475/Refrigerant Data Update>.
REFRIGERANT PHASEREFRIGERANT PHASEREFRIGERANT PHASEREFRIGERANT PHASEREFRIGERANT PHASEREFRIGERANT PHASEREFRIGERANT PHASEREFRIGERANT PHASE--------OUTOUTOUTOUTOUTOUTOUTOUT
•• 19871987
–– Montreal Protocol established Montreal Protocol established requirements that began the world wide requirements that began the world wide phasephase--out of CFCsout of CFCs
•• 19921992
–– Montreal Protocol established phaseMontreal Protocol established phase--out out for HCFCsfor HCFCs
PHASEPHASEPHASEPHASEPHASEPHASEPHASEPHASE--------OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR
HCFCSHCFCSHCFCSHCFCSHCFCSHCFCSHCFCSHCFCS
•• 2003 2003
–– The amount of all HCFCs that can be produced The amount of all HCFCs that can be produced nationwide must be reduced by 35.0% nationwide must be reduced by 35.0%
•• 20102010
–– The amount of all HCFCs that can be produced The amount of all HCFCs that can be produced nationwide must be reduced by 65.0% nationwide must be reduced by 65.0%
•• 20152015
–– The amount of all HCFCs that can be produced The amount of all HCFCs that can be produced nationwide must be reduced by 90.0%nationwide must be reduced by 90.0%
•• 20202020
–– The amount of all HCFCs that can be produced The amount of all HCFCs that can be produced nationwide must be reduced by 99.5%nationwide must be reduced by 99.5%
•• 20302030
–– No HCFCs can be producedNo HCFCs can be produced
PHASEPHASEPHASEPHASEPHASEPHASEPHASEPHASE--------OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR OUT SCHEDULE FOR
HCFCSHCFCSHCFCSHCFCSHCFCSHCFCSHCFCSHCFCS
THE USE OF CONSUMER THE USE OF CONSUMER THE USE OF CONSUMER THE USE OF CONSUMER THE USE OF CONSUMER THE USE OF CONSUMER THE USE OF CONSUMER THE USE OF CONSUMER
PREFERENCE FUNCTIONS IN PREFERENCE FUNCTIONS IN PREFERENCE FUNCTIONS IN PREFERENCE FUNCTIONS IN PREFERENCE FUNCTIONS IN PREFERENCE FUNCTIONS IN PREFERENCE FUNCTIONS IN PREFERENCE FUNCTIONS IN
REFRIGERANT DESIGNREFRIGERANT DESIGNREFRIGERANT DESIGNREFRIGERANT DESIGNREFRIGERANT DESIGNREFRIGERANT DESIGNREFRIGERANT DESIGNREFRIGERANT DESIGN
CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE
FUNCTIONS AND DEMANDFUNCTIONS AND DEMANDFUNCTIONS AND DEMANDFUNCTIONS AND DEMANDFUNCTIONS AND DEMANDFUNCTIONS AND DEMANDFUNCTIONS AND DEMANDFUNCTIONS AND DEMAND
•• In the design of the potential refrigerants, consumer preferenceIn the design of the potential refrigerants, consumer preferencefunctions were used to evaluate refrigerant properties functions were used to evaluate refrigerant properties
•• Consumer preference functions can also be used to solve for the Consumer preference functions can also be used to solve for the demand demand (d(d11) of a new refrigerant when it is in competition with an existin) of a new refrigerant when it is in competition with an existing g refrigerantrefrigerant
•• In the In the following equation, following equation, ββ is the only variable dependent on consumer is the only variable dependent on consumer preference functionspreference functions
Where: Where: Y is the market potentialY is the market potentialP is the priceP is the priceD is the demandD is the demandρρ was set to a constant value of 0.76was set to a constant value of 0.76αα is the consumer awareness of our productis the consumer awareness of our productββ relative consumer preferencerelative consumer preferenceThe subscript 1 refers to the new productThe subscript 1 refers to the new productThe subscript 2 refers to the existing comparison productThe subscript 2 refers to the existing comparison product
0)( 1
1
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112111 =
−
−=−
ρρρ
βαφ d
p
dpYpdpd
DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF αα
•• Alpha is the consumer Alpha is the consumer awareness of the new awareness of the new refrigerant as a function refrigerant as a function of time.of time.
•• The plots on the right The plots on the right show the values of alpha show the values of alpha that were used when that were used when calculating the demandcalculating the demand
•• The bottom figure The bottom figure illustrates the effect of illustrates the effect of increases advertisingincreases advertising
Alpha vs. Time
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Alpha vs. Time
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DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF DEVELOPMENT OF ββ
•• The equation used to derive The equation used to derive ββ is as followsis as follows
•• Where HWhere Hii is the respective consumer is the respective consumer preference of each productpreference of each product
Where : Where : ωωi i is the weight of refrigerant propertyis the weight of refrigerant property
yyi i is the property score of each refrigerant propertyis the property score of each refrigerant property
1
2 )(
H
preferencencompetitioH=β
∑= iii yH ω
CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE
FUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONS
•• Consumer preference functions Consumer preference functions predict consumer reactions to predict consumer reactions to different refrigerant design different refrigerant design propertiesproperties
•• The consumer preference The consumer preference functions were estimated using functions were estimated using expected consumer reactions to expected consumer reactions to refrigerant properties refrigerant properties
WHAT MAKES A GOOD WHAT MAKES A GOOD WHAT MAKES A GOOD WHAT MAKES A GOOD WHAT MAKES A GOOD WHAT MAKES A GOOD WHAT MAKES A GOOD WHAT MAKES A GOOD
REFRIGERANT?REFRIGERANT?REFRIGERANT?REFRIGERANT?REFRIGERANT?REFRIGERANT?REFRIGERANT?REFRIGERANT?
•• Safe: nonSafe: non--toxic, nonflammable, and toxic, nonflammable, and nonexplosivenonexplosive
•• Environmentally friendly: low ODP, low GWPEnvironmentally friendly: low ODP, low GWP
•• Compatible with existing refrigeration Compatible with existing refrigeration materialsmaterials
•• Desirable thermodynamic characteristics: high Desirable thermodynamic characteristics: high latent heat, low compression ratio, low specific latent heat, low compression ratio, low specific heat of liquidheat of liquid
•• Stable at operating temperaturesStable at operating temperatures
CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE
FUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONS
•• Based on 6 characteristicsBased on 6 characteristics–– FlammabilityFlammability
–– ExplosivenessExplosiveness
–– ToxicityToxicity
–– Global Warming PotentialGlobal Warming Potential
–– Ozone Depletion PotentialOzone Depletion Potential
–– Coefficient of PerformanceCoefficient of Performance
•• The outlook for discovery or synthesis of ideal The outlook for discovery or synthesis of ideal refrigerants is extremely unlikely. Traderefrigerants is extremely unlikely. Trade--offs offs among desired objectives are necessary to among desired objectives are necessary to achieve balanced solutionsachieve balanced solutions44
[4] Calm, James M. and David A. Didion. "Trade-Offs in Refrigerant Selections: Past, Present and Future." Int. J. Refrig., 21, 308 (1998).
SURVEY 1SURVEY 1SURVEY 1SURVEY 1SURVEY 1SURVEY 1SURVEY 1SURVEY 1
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Expected consumer response
ESTIMATING ESTIMATING ESTIMATING ESTIMATING ESTIMATING ESTIMATING ESTIMATING ESTIMATING ωωiiiiiiii
•• This figure represents This figure represents the expected weights of the expected weights of the refrigerant the refrigerant propertiesproperties
•• It can be seenIt can be seen
that efficiencythat efficiency
is the most is the most
important property important property
to consumersto consumers
Weighted Consumer Preferences
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`
Property Score vs. Sw eetness
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Sweet Inedible Sweetness
Property Score vs. Sw eetness
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SURVEY 2SURVEY 2SURVEY 2SURVEY 2SURVEY 2SURVEY 2SURVEY 2SURVEY 2
•• Each of the properties from Survey 1 are examined Each of the properties from Survey 1 are examined individuallyindividually
•• This Survey provides a correlation between consumer This Survey provides a correlation between consumer satisfaction and design properties satisfaction and design properties
•• Example Example –– ““Donut DesignDonut Design””
P r ope r t y S c or e v s. C onc . S uga r
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Consumer Satisfaction vs. Sweetness
SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 –––––––– EFFICIENCYEFFICIENCYEFFICIENCYEFFICIENCYEFFICIENCYEFFICIENCYEFFICIENCYEFFICIENCY
Property Score vs. Efficiency
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Property Score vs. Efficiency
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Consumer Satisfaction vs. Efficiency Property Score vs. ∆Hve/Cp
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SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 –––––––– FLAMMABILITYFLAMMABILITYFLAMMABILITYFLAMMABILITYFLAMMABILITYFLAMMABILITYFLAMMABILITYFLAMMABILITY
Property Score vs. Flash Point
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Property Score vs. Flammability
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Property Score vs. Flammability
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FlammableHighly Flammable
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Consumer Satisfaction vs. Flammability
SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 –––––––– TOXICITYTOXICITYTOXICITYTOXICITYTOXICITYTOXICITYTOXICITYTOXICITY
Property Score vs. LD50 Conc.
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Property Score vs. Toxicity
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Property Score vs. Toxicity
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Consumer Satisfaction vs. Toxicity
SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 –––––––– EXPLOSION EXPLOSION EXPLOSION EXPLOSION EXPLOSION EXPLOSION EXPLOSION EXPLOSION
POTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIAL
Property Score vs. Explosion Potential
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Property Score vs. Explosion Potential
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Property Score vs. LEL
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LEL (%)
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Consumer Satisfaction vs. Explosion Potential
SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 –––––––– GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING
POTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIAL
Property Score vs. GWP
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Property Score vs. Global Warming Potential
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Property Score vs. Global Warming Potential
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Consumer Satisfaction vs. GWP
SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 –––––––– GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING GLOBAL WARMING
POTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIALPOTENTIAL
SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 SURVEY 2 –––––––– OZONE DEPLETION OZONE DEPLETION OZONE DEPLETION OZONE DEPLETION OZONE DEPLETION OZONE DEPLETION OZONE DEPLETION OZONE DEPLETION
POTENTIAL POTENTIAL POTENTIAL POTENTIAL POTENTIAL POTENTIAL POTENTIAL POTENTIAL
Property Score vs. ODP
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Property Score vs. Ozone Depletion Potential
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Consumer Satisfaction vs. ODP
SOLVING FOR THE MARKET SOLVING FOR THE MARKET SOLVING FOR THE MARKET SOLVING FOR THE MARKET SOLVING FOR THE MARKET SOLVING FOR THE MARKET SOLVING FOR THE MARKET SOLVING FOR THE MARKET
POTENTIAL (Y)POTENTIAL (Y)POTENTIAL (Y)POTENTIAL (Y)POTENTIAL (Y)POTENTIAL (Y)POTENTIAL (Y)POTENTIAL (Y)
•• Before the market potential can be solved for, a Before the market potential can be solved for, a market must be definedmarket must be defined
•• Possible Markets for New Refrigerants Possible Markets for New Refrigerants include:include:–– Air conditioning for homes and commercial Air conditioning for homes and commercial buildingsbuildings–– Air conditioning of personal cars, trucks and Air conditioning of personal cars, trucks and sport utility vehiclessport utility vehicles–– Refrigerated transportation (food, animals, Refrigerated transportation (food, animals, beer, medical supplies etc.)beer, medical supplies etc.)–– Refrigerators and freezersRefrigerators and freezers–– Industrial operationsIndustrial operations
CENTRAL AIR/HOUSEHOLD CENTRAL AIR/HOUSEHOLD CENTRAL AIR/HOUSEHOLD CENTRAL AIR/HOUSEHOLD CENTRAL AIR/HOUSEHOLD CENTRAL AIR/HOUSEHOLD CENTRAL AIR/HOUSEHOLD CENTRAL AIR/HOUSEHOLD
UNITSUNITSUNITSUNITSUNITSUNITSUNITSUNITS
•• In 2006, the number In 2006, the number of total housing units of total housing units in the US was 124.4 in the US was 124.4 Million UnitsMillion Units
•• The number of air The number of air conditioners sold in conditioners sold in the US is estimated to the US is estimated to reach 10.7 million reach 10.7 million units in 2008units in 2008
5US Air Conditioners 2004.
AUTOMOBILES SOLD IN 2005AUTOMOBILES SOLD IN 2005AUTOMOBILES SOLD IN 2005AUTOMOBILES SOLD IN 2005AUTOMOBILES SOLD IN 2005AUTOMOBILES SOLD IN 2005AUTOMOBILES SOLD IN 2005AUTOMOBILES SOLD IN 2005
•• The automotive The automotive industry offers industry offers higher numbers of higher numbers of units sold per yearunits sold per year
•• Advantage of the Advantage of the automotive marketautomotive market
–– Higher VolumeHigher Volume
Number of cars purchased in 2005 (by country)
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ESTIMATING THE MARKET ESTIMATING THE MARKET ESTIMATING THE MARKET ESTIMATING THE MARKET ESTIMATING THE MARKET ESTIMATING THE MARKET ESTIMATING THE MARKET ESTIMATING THE MARKET
POTENTIAL OF THE AUTO MARKETPOTENTIAL OF THE AUTO MARKETPOTENTIAL OF THE AUTO MARKETPOTENTIAL OF THE AUTO MARKETPOTENTIAL OF THE AUTO MARKETPOTENTIAL OF THE AUTO MARKETPOTENTIAL OF THE AUTO MARKETPOTENTIAL OF THE AUTO MARKET
•• In this study, the automotive In this study, the automotive market was chosen because it market was chosen because it offers higher volume in salesoffers higher volume in sales
•• The market potential was The market potential was estimated by multiplying estimated by multiplying automotive sales by an average automotive sales by an average refrigerant volume required of refrigerant volume required of 24oz.24oz.
•• The answer obtained was The answer obtained was approximately 14.2 thousand approximately 14.2 thousand metric tons per yearmetric tons per year
COMPARING THIS VALUE TO COMPARING THIS VALUE TO COMPARING THIS VALUE TO COMPARING THIS VALUE TO COMPARING THIS VALUE TO COMPARING THIS VALUE TO COMPARING THIS VALUE TO COMPARING THIS VALUE TO
DATA PROVIDED BY THE DATA PROVIDED BY THE DATA PROVIDED BY THE DATA PROVIDED BY THE DATA PROVIDED BY THE DATA PROVIDED BY THE DATA PROVIDED BY THE DATA PROVIDED BY THE UNFCCCUNFCCCUNFCCCUNFCCCUNFCCCUNFCCCUNFCCCUNFCCC
•• The market potential was then compared to information The market potential was then compared to information obtained from obtained from United Nations Framework Convention on United Nations Framework Convention on Climate ChangeClimate Change (UNFCCC). The table is on the following (UNFCCC). The table is on the following slideslide
•• The UNFCCC provides the amounts of varying The UNFCCC provides the amounts of varying refrigerants produced by the participating countriesrefrigerants produced by the participating countries–– These countries are Australia, Colombia, the European These countries are Australia, Colombia, the European Union and its member states, Japan, Switzerland and the Union and its member states, Japan, Switzerland and the USA.USA.
•• Using the aforementioned estimation, it was calculated Using the aforementioned estimation, it was calculated that the US accounts for 1/10that the US accounts for 1/10thth RR--134a production cited 134a production cited by UNFCCCby UNFCCC
•• This value seems reasonable given the volume of This value seems reasonable given the volume of automobile purchased each yearautomobile purchased each year
PRODUCTION & RELEASE DATA PRODUCTION & RELEASE DATA PRODUCTION & RELEASE DATA PRODUCTION & RELEASE DATA PRODUCTION & RELEASE DATA PRODUCTION & RELEASE DATA PRODUCTION & RELEASE DATA PRODUCTION & RELEASE DATA
PROVIDED BY THE UNFCCCPROVIDED BY THE UNFCCCPROVIDED BY THE UNFCCCPROVIDED BY THE UNFCCCPROVIDED BY THE UNFCCCPROVIDED BY THE UNFCCCPROVIDED BY THE UNFCCCPROVIDED BY THE UNFCCC
HOLE IN THE OZONEHOLE IN THE OZONEHOLE IN THE OZONEHOLE IN THE OZONEHOLE IN THE OZONEHOLE IN THE OZONEHOLE IN THE OZONEHOLE IN THE OZONE
DESIGN OF NEW REFRIGERANTS DESIGN OF NEW REFRIGERANTS DESIGN OF NEW REFRIGERANTS DESIGN OF NEW REFRIGERANTS DESIGN OF NEW REFRIGERANTS DESIGN OF NEW REFRIGERANTS DESIGN OF NEW REFRIGERANTS DESIGN OF NEW REFRIGERANTS
BASED ON CONSUMER BASED ON CONSUMER BASED ON CONSUMER BASED ON CONSUMER BASED ON CONSUMER BASED ON CONSUMER BASED ON CONSUMER BASED ON CONSUMER
PREFERENCE FUNCTIONS AND PREFERENCE FUNCTIONS AND PREFERENCE FUNCTIONS AND PREFERENCE FUNCTIONS AND PREFERENCE FUNCTIONS AND PREFERENCE FUNCTIONS AND PREFERENCE FUNCTIONS AND PREFERENCE FUNCTIONS AND
THE CHOSEN MARKETTHE CHOSEN MARKETTHE CHOSEN MARKETTHE CHOSEN MARKETTHE CHOSEN MARKETTHE CHOSEN MARKETTHE CHOSEN MARKETTHE CHOSEN MARKET
METHODS FOR EXAMINING METHODS FOR EXAMINING METHODS FOR EXAMINING METHODS FOR EXAMINING METHODS FOR EXAMINING METHODS FOR EXAMINING METHODS FOR EXAMINING METHODS FOR EXAMINING
REFRIGERANTSREFRIGERANTSREFRIGERANTSREFRIGERANTSREFRIGERANTSREFRIGERANTSREFRIGERANTSREFRIGERANTS
Analysis from a listAnalysis from a list
•• Only known molecules Only known molecules can be consideredcan be considered
•• Extensive database is Extensive database is necessary for complete necessary for complete analysisanalysis
•• Limited to molecules Limited to molecules already identified as already identified as refrigerantsrefrigerants
Group contribution Group contribution theorytheory
•• Allows for the Allows for the consideration of consideration of unknown moleculesunknown molecules
•• No need for extensive No need for extensive databasesdatabases
•• Generalized approachGeneralized approach
DISCUSSION OF GROUP DISCUSSION OF GROUP DISCUSSION OF GROUP DISCUSSION OF GROUP DISCUSSION OF GROUP DISCUSSION OF GROUP DISCUSSION OF GROUP DISCUSSION OF GROUP
CONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORY
GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION
THEORYTHEORYTHEORYTHEORYTHEORYTHEORYTHEORYTHEORY
•• Developed by observation of existing Developed by observation of existing molecules as a way to predict the basic molecules as a way to predict the basic characteristics of ANY moleculecharacteristics of ANY molecule
•• Uses characteristics of each functional Uses characteristics of each functional group to estimate the characteristics of a group to estimate the characteristics of a molecule formed from the functional molecule formed from the functional groupsgroups
MOLECULE MADE OF MOLECULE MADE OF MOLECULE MADE OF MOLECULE MADE OF MOLECULE MADE OF MOLECULE MADE OF MOLECULE MADE OF MOLECULE MADE OF
FUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPS
•• Specific groups of Specific groups of atoms within a atoms within a moleculemolecule
•• Responsible for the Responsible for the chemical makechemical make--up of up of the moleculethe molecule
•• Example: Example:
–– 3 different 3 different functional group functional group typestypes
–– 6 total groups6 total groups1,1,1,2-Tetrafluoroethane
FUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPSFUNCTIONAL GROUPS
=O=O
--COOCOO--=C==C=
--NO2NO2--COOHCOOH=C<=C<
--CNCN--CHOCHO=CH=CH--
R=NR=N--2R>CO2R>COR=C<2RR=C<2R=CH2=CH2
>N>N-->CO>CO--IIR=CHR=CH--RR>C<>C<
RR--SS--RR2R>NH2R>NHRR--OO--RR--BrBr2R>C<2R2R>C<2R>CH>CH--
--SS-->NH>NH--OO----ClCl2R>CH2R>CH--RR--CH2CH2--
--SHSH--NH2NH2--OHOH--FFRR--CH2CH2--RR--CH3CH3
Sulfur Sulfur GroupsGroups
Nitrogen Nitrogen GroupsGroups
Oxygen Oxygen GroupsGroups
Halogen Halogen GroupsGroups
Cyclic Cyclic GroupsGroups
Acyclic Acyclic GroupsGroups
= represents a double bond, bonding site
-- represents a single bond, bonding site
R represents a ring bonding site
ENUMERATION MODELING IN ENUMERATION MODELING IN ENUMERATION MODELING IN ENUMERATION MODELING IN ENUMERATION MODELING IN ENUMERATION MODELING IN ENUMERATION MODELING IN ENUMERATION MODELING IN
EXCEL USING GROUP EXCEL USING GROUP EXCEL USING GROUP EXCEL USING GROUP EXCEL USING GROUP EXCEL USING GROUP EXCEL USING GROUP EXCEL USING GROUP
CONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORY
ENUMERATION VS. ENUMERATION VS. ENUMERATION VS. ENUMERATION VS. ENUMERATION VS. ENUMERATION VS. ENUMERATION VS. ENUMERATION VS.
OPTIMIZATIONOPTIMIZATIONOPTIMIZATIONOPTIMIZATIONOPTIMIZATIONOPTIMIZATIONOPTIMIZATIONOPTIMIZATION
EnumerationEnumeration
•• No initial guess requiredNo initial guess required
•• Calculates every possible Calculates every possible optionoption
•• Complete confidence in Complete confidence in solutionsolution
•• Very time consumingVery time consuming ––requires hours or days requires hours or days for processingfor processing
Optimization ModelOptimization Model
•• Requires a good initial Requires a good initial guessguess
•• Calculates only options Calculates only options which lead to a more which lead to a more likely solutionlikely solution
•• Almost complete Almost complete confidence in solutionconfidence in solution
•• Less time consuming Less time consuming ––requires a few hours for requires a few hours for
processingprocessing
WHAT IS THE ENUMERATION WHAT IS THE ENUMERATION WHAT IS THE ENUMERATION WHAT IS THE ENUMERATION WHAT IS THE ENUMERATION WHAT IS THE ENUMERATION WHAT IS THE ENUMERATION WHAT IS THE ENUMERATION
METHOD?METHOD?METHOD?METHOD?METHOD?METHOD?METHOD?METHOD?
•• Also known as the exhaustive method or brute force Also known as the exhaustive method or brute force methodmethod
•• Take into account every possible combination of Take into account every possible combination of functional groupsfunctional groups
-CH3 n-CH3 = 0 1 2
-CH2- n-CH2-= 0 1 2 0 1 2 0 1 2
>CH- n>CH-= 0 1 2 0 1 2 0 1 2 0 1 2 0 1 2 0 1 2 0 1 2 0 1 2 0 1 2
Iterations for 3x3 = 27
VBA CODEVBA CODEVBA CODEVBA CODEVBA CODEVBA CODEVBA CODEVBA CODE
VBA CODEVBA CODEVBA CODEVBA CODEVBA CODEVBA CODEVBA CODEVBA CODE
VBA CODEVBA CODEVBA CODEVBA CODEVBA CODEVBA CODEVBA CODEVBA CODE
REFRIGERANT MODELINGREFRIGERANT MODELINGREFRIGERANT MODELINGREFRIGERANT MODELINGREFRIGERANT MODELINGREFRIGERANT MODELINGREFRIGERANT MODELINGREFRIGERANT MODELING
Our designOur design
1.1. Design Basic Thermodynamic Design Basic Thermodynamic OptimizationOptimization
2.2. Include structural constraintsInclude structural constraints
3.3. Include physical constraintsInclude physical constraints
4.4. Find information on existing Find information on existing moleculesmolecules
5.5. Select molecules for further researchSelect molecules for further research
FLOW OF VARIABLES FROM FLOW OF VARIABLES FROM FLOW OF VARIABLES FROM FLOW OF VARIABLES FROM FLOW OF VARIABLES FROM FLOW OF VARIABLES FROM FLOW OF VARIABLES FROM FLOW OF VARIABLES FROM
GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION GROUP CONTRIBUTION
THEORYTHEORYTHEORYTHEORYTHEORYTHEORYTHEORYTHEORY
HOW TO USE GROUP HOW TO USE GROUP HOW TO USE GROUP HOW TO USE GROUP HOW TO USE GROUP HOW TO USE GROUP HOW TO USE GROUP HOW TO USE GROUP
CONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORY
Tb=Boiling temperatureTb=Boiling temperatureTbi=contribution of group i to Tbi=contribution of group i to
boiling temperatureboiling temperatureTc=critical temperatureTc=critical temperatureTci= contribution of group i to critical Tci= contribution of group i to critical temperaturetemperature
ai=number of atoms in group iai=number of atoms in group iPci= contribution of group i to critical Pci= contribution of group i to critical pressurepressure
Tavg= average temperature (user Tavg= average temperature (user defined)defined)
Cp0ai=Cp0ai=a a contribution to heat contribution to heat capacity capacity
Cp0bi=Cp0bi=b b contribution to heat contribution to heat capacity capacity
Cp0ci=Cp0ci=c c contribution to heat contribution to heat capacity capacity
Cp0di=Cp0di=d d contribution to heat contribution to heat capacity capacity at average at average
temperature temperature *** Equations 1*** Equations 1--4 are the only ones 4 are the only ones dependent upon values of nidependent upon values of ni
3
1
70
2
1
40
10
100
*10*06.2*
*10*91.3*
*21.0*93.37*
avg
N
idipi
avg
N
icipi
avg
N
ibipi
N
iaipiap
TCn
TCn
TCnCnC
−+
−+
−+−=
∑
∑
∑∑
=
−
=
−
==
2
1 1
***0032.0113.0
1
−+
=
∑ ∑= =
N
i
N
iciiii
c
Pnan
P
∑ ∑= =
−+
=N
i
N
iciicii
bc
TnTn
TT
1
2
1
***965.0584.0(
∑=
+=N
ibiib TnT
1
*21.198
THERMODYNAMIC THERMODYNAMIC THERMODYNAMIC THERMODYNAMIC THERMODYNAMIC THERMODYNAMIC THERMODYNAMIC THERMODYNAMIC
EQUATIONSEQUATIONSEQUATIONSEQUATIONSEQUATIONSEQUATIONSEQUATIONSEQUATIONS•• Liquid Heat Capacity at TLiquid Heat Capacity at Tavgavg
•• Heat of vaporization at boiling temperature (Riedel Heat of vaporization at boiling temperature (Riedel Method)Method)
•• Heat of vaporization at evaporation temperatureHeat of vaporization at evaporation temperature
( )( )
−+
−++
−++=
avgravgr
avgr
avgrappla TT
T
TCC
1
742.11*2.2511.17**25.0
1
45.045.1*314.8*
1868.4
13/1
0 ω
( )
−−
=∆br
cbrcvb T
PTTRH
930.0
013.1ln****093.1
38.0
1
1*
−−
∆=∆cb
cevpvbve TT
TTHH
PRESSURE EQUATIONSPRESSURE EQUATIONSPRESSURE EQUATIONSPRESSURE EQUATIONSPRESSURE EQUATIONSPRESSURE EQUATIONSPRESSURE EQUATIONSPRESSURE EQUATIONS
•• Vapor pressure at condensing Vapor pressure at condensing
•• Vapor pressure at evaporationVapor pressure at evaporation
( ) ( )( )[ ]32 13*1*ln cndrcndrcndrcndr
vpcr TTkTT
GP −++−−=
( ) ( )( )[ ]32 13*1*ln evprevprevprevpr
vper TTkTT
GP −++−−=
cvpcrvpc PPP *=
cvpervpe PPP *=
GROUP COMBINATION GROUP COMBINATION GROUP COMBINATION GROUP COMBINATION GROUP COMBINATION GROUP COMBINATION GROUP COMBINATION GROUP COMBINATION
CONSTRAINTS CONSTRAINTS CONSTRAINTS CONSTRAINTS CONSTRAINTS CONSTRAINTS CONSTRAINTS CONSTRAINTS
1.1. Structural feasibilityStructural feasibility
2.2. Size and molecular weightSize and molecular weight
3.3. Vapor pressureVapor pressure
STRUCTURAL FEASIBILITYSTRUCTURAL FEASIBILITYSTRUCTURAL FEASIBILITYSTRUCTURAL FEASIBILITYSTRUCTURAL FEASIBILITYSTRUCTURAL FEASIBILITYSTRUCTURAL FEASIBILITYSTRUCTURAL FEASIBILITY
•• Even number of groups with odd number of Even number of groups with odd number of bonding sitesbonding sites•• 2 2 ““--CH3CH3”” groups or 1 groups or 1 ““--CH3CH3”” group and 1 group and 1 ““>CH>CH--”” groupgroup
•• Groups must be able to connect to form Groups must be able to connect to form ONE moleculeONE molecule•• 2 2 ““--CH3CH3”” groups cannot connect with 2 groups cannot connect with 2 ““--FF””groups to make ONE moleculegroups to make ONE molecule
•• Total number of bonding sites should be Total number of bonding sites should be eveneven•• 2 bonding sites make 1 bond2 bonding sites make 1 bond
STRUCTURAL FEASIBILITY STRUCTURAL FEASIBILITY STRUCTURAL FEASIBILITY STRUCTURAL FEASIBILITY STRUCTURAL FEASIBILITY STRUCTURAL FEASIBILITY STRUCTURAL FEASIBILITY STRUCTURAL FEASIBILITY
CONCONCONCONCONCONCONCON’’’’’’’’DDDDDDDD
•• Number of each bonding type should be even Number of each bonding type should be even •• 2 2 ““=CH2=CH2”” groups, 2 groups, 2 ““=O=O”” groups, or 1 groups, or 1 ““=CH2=CH2”” with 1 with 1 ““=C==C=”” with 1 with 1 ““=O=O”” groupgroup
•• Mixed bonding types should have a transition Mixed bonding types should have a transition groupgroup
•• 1 1 ““=CH2=CH2”” and 1 and 1 ““--FF”” requires 1 requires 1 ““=CH=CH--”” groupgroup
•• Every branch should have an edge (end cap)Every branch should have an edge (end cap)•• Example: 1 Example: 1 ““>C<>C<”” group have 4 branches which will group have 4 branches which will require 4 groups with only 1 bonding site such as require 4 groups with only 1 bonding site such as ““--FF””
MOLECULAR SIZEMOLECULAR SIZEMOLECULAR SIZEMOLECULAR SIZEMOLECULAR SIZEMOLECULAR SIZEMOLECULAR SIZEMOLECULAR SIZE
•• Minimum number of groups is 2Minimum number of groups is 2
•• Maximum number of groups is 10Maximum number of groups is 10–– Max groups by type:Max groups by type:
one bond = 7 one bond = 7 –– CC--CHCH--C(F)C(F)77=10=10
two bonds = 8 two bonds = 8 –– CHCH33--(CH(CH22))88--CHCH33=10 =10
three bonds = 4 three bonds = 4 –– (CH)(CH)44(F)(F)66=10=10
four bonds = 2 four bonds = 2 –– (C)(C)33(F)(F)88=11=11
•• Our results show that the maximum number of Our results show that the maximum number of groups used is 9groups used is 9
•• Typically larger molecules have higher boiling Typically larger molecules have higher boiling points making them unfit for refrigerationpoints making them unfit for refrigeration
VAPOR PRESSUREVAPOR PRESSUREVAPOR PRESSUREVAPOR PRESSUREVAPOR PRESSUREVAPOR PRESSUREVAPOR PRESSUREVAPOR PRESSURE
•• Minimum vapor pressure at evaporation Minimum vapor pressure at evaporation temperature of 1 bartemperature of 1 bar
–– Atmospheric pressureAtmospheric pressure
•• Maximum vapor pressure at Maximum vapor pressure at condensation of 10 barcondensation of 10 bar
–– Mechanical compressibility factorMechanical compressibility factor
–– MultiMulti--stage compressor (cost prohibitive)stage compressor (cost prohibitive)
•• Heat capacity must be positiveHeat capacity must be positive
–– Negative heat capacity is not possible Negative heat capacity is not possible physicallyphysically
““““““““MAKINGMAKINGMAKINGMAKINGMAKINGMAKINGMAKINGMAKING”””””””” A MOLECULEA MOLECULEA MOLECULEA MOLECULEA MOLECULEA MOLECULEA MOLECULEA MOLECULE
•• nn--F F = 2= 2
•• nn--Cl Cl = 2= 2
•• nn>C< >C< = 1= 1
•• FreonFreon
•• nn--------CH3CH3CH3CH3CH3CH3CH3CH3 = 2= 2
•• nn--CH2CH2--= 2= 2
•• ButaneButane
•• nn--CH3 CH3 = 3= 3
•• nn>CH>CH--= 1= 1
•• isoiso--butanebutane
•• nn--CH3 CH3 = 2= 2
•• nn>CH>CH-- = 1= 1
•• nn--CH2CH2--= 1= 1
•• nn--OH OH = 1= 1
•• isoiso--butanolbutanol
•• nn=CH2 =CH2 = 1= 1
•• nn=C< =C< = 1= 1
•• nn--OO-- = 1= 1
•• nn--F F = 2= 2
•• ????
MOLECULE MAKERMOLECULE MAKERMOLECULE MAKERMOLECULE MAKERMOLECULE MAKERMOLECULE MAKERMOLECULE MAKERMOLECULE MAKER
n= Pvpe FALSE 0 Tavg K 294sCH3 2 Pvpc FALSE 0 Tevp K 272
sCH2s 2 heatcap TRUE 1 Tcnd K 317ssCHs 2 0 N groups 6ssCss 0 Tboil K 334.61dCH2 0 Ynt true 1 Tcrit K 499.73 dCHs 0 oddfree true 1 Pcrit bar 35.01 dCss 0 connected true 1 heatcap J/molK 0.131dCd 0 nofree true 1 Tb reduced 0.670
rCH2r 0 bond type true 1 Tavg reduced K 0.588rrCHr 0 singlefree true 1 Tcnd reduced 0.633rrCrr 0 double free true 1 Tevp reduced 0.544
drCHr 0 triple free true 1 alpha -0.942drCrr 0 single cyclic free true 1 beta -2.734sF 0 double cyclic free true 1 omega 0.345sCl 0 mixed true 1 heat capacity J/molK 45.325sBr 0 end cap false 0 enthalpy of vaporization boil tempkJ/mol 29.502sI 0 real structure 0 enthalpy of vaporization evap tempkJ/mol 33.335
sOH 0 h 7.179sOs 0 Yss 1 G 3.790rOr 0 Ydd 0 ka 0.561
ssCO 0 Ytt 0 Pvpcr 0.015rrCO 0 Ysr 0 Pvper 0.002
sCHO 0 Ydr 0 Pvpc bar 0.533sCOOH 0 Yr 0 Pvpe bar 0.070sCOOs 0 Ysd 0 t= 0.000
doO 0 Yst 0sNH2 0 Yssr 0ssNH 0 Ysdr 0rrNH 0 Ydsr 0 iterationsssNs 0 Y0m 1 27drNs 0 Ym5 0sCN 0 Ym1 1
sNO2 0 Ym6 0sSH 0 Ym2 1sSs 0 Ym7 0rSr 0 Ym3 1
6 Ym8 0Ym4 1Ym9 0
Binary Variables
Physical Constraints Thermodynamic Properties
Structural Constraints
RESULTS FROM EXCELRESULTS FROM EXCELRESULTS FROM EXCELRESULTS FROM EXCELRESULTS FROM EXCELRESULTS FROM EXCELRESULTS FROM EXCELRESULTS FROM EXCEL
•• 3,692,945 possible solutions (16 hours)3,692,945 possible solutions (16 hours)
•• 649 solutions649 solutions
•• 566 structurally feasible solutions (passed the 566 structurally feasible solutions (passed the filter, but not feasible)filter, but not feasible)
•• Since each solution was evaluated by Since each solution was evaluated by referencing online databases the process for referencing online databases the process for finding molecules was extremely tediousfinding molecules was extremely tedious
•• are included in optimization function are included in optimization function calculations for comparisoncalculations for comparison
ββ VALUESVALUESVALUESVALUESVALUESVALUESVALUESVALUES
•• Using the preceding six quantitative plots, a value for Using the preceding six quantitative plots, a value for ββfor each possible refrigerant can be definedfor each possible refrigerant can be defined
Chemical Formula H = Σxiyij β = H2/H1 Rank
CH2=CH-F 0.61 1.39 2CH3 -CH=CH2 0.61 1.39 4
CH2=CF2 0.51 1.68 8CH2=CH-Cl 0.50 1.69 1CH2=CFCl 0.49 1.75 3
CH2=C=CH-F 0.40 2.13 5CH2=CH-O-F 0.40 2.14 6
CH2=CH-C(=O)-F 0.40 2.14 20Cl2 0.40 2.15 7F-Br 0.39 2.17 9
CH2=CCH3F 0.39 2.17 10CH2=CH-CH2-F 0.39 2.18 11
CH2=C=CF2 0.39 2.18 12CH2=C=C=C=O 0.39 2.19 13
FSH 0.39 2.19 14CH2=C(-F)-O-F 0.39 2.19 15
FNH2 0.39 2.19 16cyc(CH=CH-CH2) 0.39 2.19 17
cyc(CH=CH-O) 0.39 2.20 18O=CH-Br 0.38 2.22 19
R134a 0.85 1.00 -
LIMITATIONS OF GROUP LIMITATIONS OF GROUP LIMITATIONS OF GROUP LIMITATIONS OF GROUP LIMITATIONS OF GROUP LIMITATIONS OF GROUP LIMITATIONS OF GROUP LIMITATIONS OF GROUP
CONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORYCONTRIBUTION THEORY
•• Actual data compared with data found using functional Actual data compared with data found using functional group theory group theory
abs(Tabs(Tb(theory)b(theory)--TTb(act)b(act))= )= ∆∆TTbb
•• Average Average ∆∆TTbb = 39.7K= 39.7K
•• Examples: Examples:
33--fluorofluoro--11--propene, min propene, min ∆∆TTbb=1.2K=1.2K
11--fluorofluoro--22--propanonepropanone, max , max ∆∆TTbb=89.9K=89.9K
12%12%14%14%16%16%averageaverage
0.5%0.5%1.1%1.1%0.4%0.4%minmin
36%36%32%32%47%47%maxmax
PPcritcritTTcritcritTTboilboil
ERROERRORR
LIMITATIONS OF FUNCTIONAL LIMITATIONS OF FUNCTIONAL LIMITATIONS OF FUNCTIONAL LIMITATIONS OF FUNCTIONAL LIMITATIONS OF FUNCTIONAL LIMITATIONS OF FUNCTIONAL LIMITATIONS OF FUNCTIONAL LIMITATIONS OF FUNCTIONAL
GROUP THEORYGROUP THEORYGROUP THEORYGROUP THEORYGROUP THEORYGROUP THEORYGROUP THEORYGROUP THEORY
•• Errors reveal inconsistencies with Errors reveal inconsistencies with functional group theoryfunctional group theory
•• Possibly good refrigerants were likely Possibly good refrigerants were likely excluded from our findingsexcluded from our findings
RECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONS
RECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONS
1.1. Develop correlations to relate data obtained from models to Develop correlations to relate data obtained from models to consumer preference functions. Relationships could be consumer preference functions. Relationships could be developed to relate properties that can be found from the developed to relate properties that can be found from the empirical data to those exclusive to an individual molecule. empirical data to those exclusive to an individual molecule.
2.2. Link spreadsheets to databases to quickly search through Link spreadsheets to databases to quickly search through molecules. Not all properties can be examined from a molecules. Not all properties can be examined from a moleculemolecule’’s empirical formula or structure. Many s empirical formula or structure. Many databases, in periodicals, for potential refrigerant databases, in periodicals, for potential refrigerant molecules are available for possible refrigerants. These molecules are available for possible refrigerants. These databases could eliminate error caused by property databases could eliminate error caused by property estimation. estimation.
3.3. A large scale survey needs to be performed. A large scale A large scale survey needs to be performed. A large scale random survey is needed to find actual consumer random survey is needed to find actual consumer preferences to refrigerant properties. preferences to refrigerant properties.
RECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONSRECOMMENDATIONS
3.3. More structural constraints need to be More structural constraints need to be developed. Some molecular structures pass developed. Some molecular structures pass the filters in the iterative method, but do not the filters in the iterative method, but do not exist in reality.exist in reality.
4.4. Considering refrigerant blends would create Considering refrigerant blends would create many more options for refrigerant solutions.many more options for refrigerant solutions.
5.5. Laboratory study Laboratory study -- The laboratory setting The laboratory setting offers the benefit of being able to measure offers the benefit of being able to measure properties for synthesized refrigerants. In properties for synthesized refrigerants. In this way, more accurate correlations for this way, more accurate correlations for group contributions or efficiency could be group contributions or efficiency could be developed.developed.
QUESTIONS?QUESTIONS?QUESTIONS?QUESTIONS?QUESTIONS?QUESTIONS?QUESTIONS?QUESTIONS?
WORKS CITEDWORKS CITEDWORKS CITEDWORKS CITEDWORKS CITEDWORKS CITEDWORKS CITEDWORKS CITED
1.1. History of the Refrigerator. History of the Refrigerator. History.com. 2/7/2007 History.com. 2/7/2007 <<http://www.history.com/exhibits/modern/fridge.htmlhttp://www.history.com/exhibits/modern/fridge.html>.>.
2.2. Refrigerant Data UpdateRefrigerant Data Update. January 2007. Heating/Piping/Air . January 2007. Heating/Piping/Air Conditioning Engineering. Feb. 7, 2007 Conditioning Engineering. Feb. 7, 2007 <<http://www.hpac.com/Issue/Article/44475/Refrigerant_Data_Updatehttp://www.hpac.com/Issue/Article/44475/Refrigerant_Data_Update>.>.
3.3. What you Should Know about Refrigerants when Purchasing or What you Should Know about Refrigerants when Purchasing or Repairing a Residential A/C System or Heat Pump. Repairing a Residential A/C System or Heat Pump. Jan. 29, 2007. Jan. 29, 2007. Environmental Protection Agency. Jan. 29Environmental Protection Agency. Jan. 29thth, 2007 , 2007 <<http://www.epa.gov/ozone/title6/phaseout/22phaseout.htmlhttp://www.epa.gov/ozone/title6/phaseout/22phaseout.html>.>.
4.4. HCFC Phaseout Schedule. HCFC Phaseout Schedule. April 16April 16thth, 2006. Environmental Protection , 2006. Environmental Protection Agency. Feb. 5Agency. Feb. 5thth, 2007 , 2007 <<http://www.epa.gov/ozone/title6/phaseout/hcfc.htmlhttp://www.epa.gov/ozone/title6/phaseout/hcfc.html>.>.
5.5. Air Conditioners 2004. Air Conditioners 2004. July 2004.July 2004. Snapshot International. Feb. 11Snapshot International. Feb. 11thth, , 2007 <2007 <http://dx.doi.org/10.1337/us080034http://dx.doi.org/10.1337/us080034>.>.
6.6. American Housing Survey for the United States: 2005.American Housing Survey for the United States: 2005. August 2006. August 2006. U.S. Department of Housing and Urban Development and the US U.S. Department of Housing and Urban Development and the US Department of Commerce. Feb 11Department of Commerce. Feb 11thth, 2007 , 2007 <<http://www.census.gov/prod/2006pubs/h150http://www.census.gov/prod/2006pubs/h150--05.pdf05.pdf>.>.
7.7. Trends in Residential AirTrends in Residential Air--Conditioning Usage from 1978 to 1997.Conditioning Usage from 1978 to 1997. July July 24, 2000. US Department of Energy. Feb 1124, 2000. US Department of Energy. Feb 11thth, 2007 , 2007 <<http://www.eia.doe.gov/emeu/consumptionbriefs/recs/actrends/recshttp://www.eia.doe.gov/emeu/consumptionbriefs/recs/actrends/recs_ac_t_ac_trends.htmlrends.html>.>.
8.8. The Properties of Gases and Liquids 5The Properties of Gases and Liquids 5thth Edition. Edition. OO’’Connell, J., B. Poling Connell, J., B. Poling and J. Pransnite.McGrawand J. Pransnite.McGraw--Hill, New York, 2001. Chapter 2 (78Hill, New York, 2001. Chapter 2 (78--89).89).
APPENDIXAPPENDIXAPPENDIXAPPENDIXAPPENDIXAPPENDIXAPPENDIXAPPENDIX
CREATING MORE ACCURATE CREATING MORE ACCURATE CREATING MORE ACCURATE CREATING MORE ACCURATE CREATING MORE ACCURATE CREATING MORE ACCURATE CREATING MORE ACCURATE CREATING MORE ACCURATE
CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE CONSUMER PREFERENCE
FUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONSFUNCTIONS
•• To accurately predict the refrigerant To accurately predict the refrigerant market, a large scale survey needs to be market, a large scale survey needs to be performedperformed
•• The large scale survey will eliminate The large scale survey will eliminate inaccuracies present in the survey inaccuracies present in the survey prepared and presented previouslyprepared and presented previously
•• These inaccuracies stem from the These inaccuracies stem from the inherent bias in a small surveyinherent bias in a small survey
MORE THERMODYNAMIC MORE THERMODYNAMIC MORE THERMODYNAMIC MORE THERMODYNAMIC MORE THERMODYNAMIC MORE THERMODYNAMIC MORE THERMODYNAMIC MORE THERMODYNAMIC
EQUATIONSEQUATIONSEQUATIONSEQUATIONSEQUATIONSEQUATIONSEQUATIONSEQUATIONS
( ) 6*169347.0ln*28862.109648.6
013.1ln97214.5 brbr
br
c TTT
P−++
−−=α
( ) 6*43577.0ln*4721.136875.15
2518.15 brbrbr
TTT
+−−=β
βαω =
( )br
cbr
T
PTh
−=
1
013.1ln*
hG *4605.04835.0 +=
( )( )( )213
1
brbr
br
TT
TGhk
−++−
=
THERMODYNAMICSTHERMODYNAMICSTHERMODYNAMICSTHERMODYNAMICSTHERMODYNAMICSTHERMODYNAMICSTHERMODYNAMICSTHERMODYNAMICS
•• Functional group theory can be used to Functional group theory can be used to determine many important determine many important characteristicscharacteristics
•• TemperatureTemperature--Entropy data are needed Entropy data are needed to accurately determine efficiency, but to accurately determine efficiency, but cannot be determined from functional cannot be determined from functional group theorygroup theory
•• ∆∆H/CH/Cpp is used to estimate efficiencyis used to estimate efficiency
GAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODE
GAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODE
GAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODE
GAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODEGAMS CODE
SYSTEMATIC DESIGNSYSTEMATIC DESIGNSYSTEMATIC DESIGNSYSTEMATIC DESIGNSYSTEMATIC DESIGNSYSTEMATIC DESIGNSYSTEMATIC DESIGNSYSTEMATIC DESIGN
ENVIRONMENTAL EFFECTSENVIRONMENTAL EFFECTSENVIRONMENTAL EFFECTSENVIRONMENTAL EFFECTSENVIRONMENTAL EFFECTSENVIRONMENTAL EFFECTSENVIRONMENTAL EFFECTSENVIRONMENTAL EFFECTS
•• Ozone depletion potentialOzone depletion potential
–– Only heavy halogens are known to Only heavy halogens are known to contributecontribute
•• Global warming potentialGlobal warming potential
–– Requires experiments to find radiative Requires experiments to find radiative efficiency and time dependent decayefficiency and time dependent decay
) / exp(-3.858*)(n 0.05013 ODP 1.510Cl τ=
OBTAINING VALUES FOR THE OBTAINING VALUES FOR THE OBTAINING VALUES FOR THE OBTAINING VALUES FOR THE OBTAINING VALUES FOR THE OBTAINING VALUES FOR THE OBTAINING VALUES FOR THE OBTAINING VALUES FOR THE
OBJECTIVE FUNCTIONOBJECTIVE FUNCTIONOBJECTIVE FUNCTIONOBJECTIVE FUNCTIONOBJECTIVE FUNCTIONOBJECTIVE FUNCTIONOBJECTIVE FUNCTIONOBJECTIVE FUNCTION
•• Flammability and Flammability and explosivenessexplosiveness
–– Based on lower Based on lower explosive limitexplosive limit
–– Based on vapor pressureBased on vapor pressure
–– No strong correlationNo strong correlation
•• Toxicity Toxicity
–– Based on experimental Based on experimental resultsresults
–– Found only for existing Found only for existing moleculesmolecules
Vapor Pressure vs. LELy = 176.5x - 29.778
R2 = 0.0351
-5000
0
5000
10000
15000
20000
25000
30000
35000
0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1
LEL (%)
Vap
or
Pre
ssure
(mm
Hg
)
Flash Point vs. LEL
Lineary = -66.281x + 68.752
R2 = 0.4087
3rd Order Polynomial
y = 50.242x3 - 231x2 + 275.14x - 92.641
R2 = 0.4151
6th Order Polynomial
y = -1196.1x6 + 9953.1x5 - 34677x4 + 65066x3 - 69409x2 + 39657x - 9368.3
R2 = 0.5702
-120
-100
-80
-60
-40
-20
0
20
40
0 0.5 1 1.5 2 2.5
LEL (%)
Fla
sh P
oin
t (oC
)
CORRELATION WITH CORRELATION WITH CORRELATION WITH CORRELATION WITH CORRELATION WITH CORRELATION WITH CORRELATION WITH CORRELATION WITH
MOLECULAR WEIGHTMOLECULAR WEIGHTMOLECULAR WEIGHTMOLECULAR WEIGHTMOLECULAR WEIGHTMOLECULAR WEIGHTMOLECULAR WEIGHTMOLECULAR WEIGHT
y = -0.0095x + 1.749
R2 = 0.9276
0.3
0.5
0.7
0.9
1.1
1.3
50 75 100 125 150molecular wieght
dH
/Cp
average comparison
∆∆∆∆∆∆∆∆H/CH/CH/CH/CH/CH/CH/CH/CPPPPPPPP CORRELATION WITH CORRELATION WITH CORRELATION WITH CORRELATION WITH CORRELATION WITH CORRELATION WITH CORRELATION WITH CORRELATION WITH
COPCOPCOPCOPCOPCOPCOPCOP
Correlation of dH/Cp with COP
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0 1 2 3 4 5
COP (PRO/II)
dH
/Cp dH/Cp
Poly. (dH/Cp)
EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR
NEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTS
•• The following journal publications The following journal publications describe in detail how the COP for new describe in detail how the COP for new refrigerants can be evaluatedrefrigerants can be evaluated
1.1. Fleming, John S., Alex C. Bwalya and William Dempster. Fleming, John S., Alex C. Bwalya and William Dempster. ““The testing and evaluation of trial refrigerants: Part 1. The testing and evaluation of trial refrigerants: Part 1. System description.System description.”” International Journal of Energy International Journal of Energy Research Research 24.14 (2000): 121724.14 (2000): 1217--1241.1241.
2.2. Fleming, John S., Alex C. Bwalya and William Dempster. Fleming, John S., Alex C. Bwalya and William Dempster. ““The testing and evaluation of trial refrigerants: Part 2. The testing and evaluation of trial refrigerants: Part 2. The practical use of measured data.The practical use of measured data.”” International International Journal of Energy Research Journal of Energy Research 24.14 (2000): 124324.14 (2000): 1243--1256.1256.
EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR EVALUATING THE COP FOR
NEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTSNEW REFRIGERANTS
•• Following a similar procedure, outlined in Following a similar procedure, outlined in these two articles, would provide the COP for these two articles, would provide the COP for the tested refrigerantsthe tested refrigerants
•• Then a correlation could be developed to relate Then a correlation could be developed to relate the COP to functional group contributionsthe COP to functional group contributions
•• This correlation would allow for a more This correlation would allow for a more rigorous analysis of all the possible rigorous analysis of all the possible refrigerantsrefrigerants
•• The refrigerants could then be ranked and The refrigerants could then be ranked and analyzed using more accurate consumer analyzed using more accurate consumer preference functionspreference functions