m(antreal protocol 22777 -...
TRANSCRIPT
M(ANTREALPROTOCOL
22777The Availability of Hydrocarbons for
ODS Phaseout inDeveloping Countries
OORGPRODUCTION SECTOR WORKING GROUP
OZONE OPERATIONS RESOURCE GROUPREPORT NUMBER 12
APRIL 1995
THE WORLD BANK
GLOBAL ENVIRONMENT COORDINATION DIVISIONENVIRONMENT DEPARTMENT
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The Availability of Hydrocarbons forODS Phaseout in
Developing Countries
OORGPRODUCTION SECTOR WORKING GROUP
OZONE OPERATIONS RESOURCE GROUPREPORT NUMBER 12
APRIL 1995
CONTENTS
Page
Preface ...................................................... i
The Availability of Hydrocarbons for ODS Phaseout in Developing Countries . ...............................1
APPENDIX I Hydrocarbons S tudy Report ...................................................... 4
APPENDIX II OORG Publications List .29
PREFACE
As sector-specific problems and issues arise and are identified as needing additional or specialattention, OORG Working Groups are established under the coordination of the relevant OORG SectorAdvisor and are comprised of technical experts from companies, laboratories and applied researchinstitutions on the leading edge of technological developments in industry around the world. Working Groupexpert participants to date have included individuals from a growing number of developing countries, amongthem, Brazil, China, and India. OORG Working Groups prepare and periodically update sectoral overviewpapers and recommendations as guidance to Bank task managers and client developing countries in preparinginvestment projects for financing through the Montreal Protocol and the Global Environment Facility.
As of 1995, six OORG sector working groups have been assembled and prepared an assortment ofsector-specific overview papers and associated definitive recommendations and guidance to the Bank and itsclients', namely: (1) the OORG Refrigeration Working Group, (2) the OORG Refrigeration/FreezerInsulating Foam Working Group, (3) the OORG Foam Pre-insulated Pipes Working Group, (4) the OORGProduction Alternatives Working Group, (5) the OORG Chiller Working Group, and (6) the OORG MobileAir Conditioning System (MACS) Working Group.2
X This particular report, OORG Report No. 12, was prepared under the overall direction of Dr. Michael Harris, of ICI Klea, Runcom, U.K.Dr. Harris is the OORG Production Sector Advisor to the World Bank and Chairman of the OORG Production Working Group. The study was ledby Mr. Brian Joyner, OORG Production Sector First Peer, Regulatory and Technical Resources, Bristol, U.K., in collaboration with Mr. GregoryCollins, Phillips Chemical Co., Bartdesville, OK, USA and Dr. Harris.
2 See present list of OORG publications, Appendix 11.
Ozone Operations Resource Group(OORG)
THE AVAILABILITY OF HYDROCARBONSFOR ODS PHASEOUT IN DEVELOPING COUNTRIES
1. Backeround
The Ozone Operations Resource Group (OORG) was assembled by the World Bank to providespecialized sector-based technical advice and assistance to the Bank in fulfilling its role as one of the fourprincipal implementing agencies (with UNDP, UNEP and UNIDO) of the Multilateral Fund under theMontreal Protocol (MFMP). Within the context of the Bank's assistance to the developing countries toprepare Country Programs and investment projects for the phaseout of ozone depleting substances (ODS),the OORG keeps the Bank apprised of applicable sector-specific technological advances, commerciallyavailable ODS substitutes, the cost-effectiveness of the various sectoral options, and related developments.
Both the OORG Refrigeration Working Group and the OORG Refrigerator/Foam Working Group,following back-to-back meetings in May 1994, recommended that the future availability and cost/price ofhydrocarbons in developing countries be addressed in relation to required levels of chemnical quality by theOORG Production Working Group. Similar concerns were voiced in the aerosol sector as a result offindings generated by the Bank's Global Aerosol Project. During the Sixth OORG Meeting on October 27,1994, it was agreed that OORG Production Sector Advisor, Dr. Michael Harris, would convene a specialplanning meeting in November 1994 in order to organize a study of these issues on the key relatedhydrocarbons, including for example: propane/butane (HAP grade), n-butane, iso-butane, and cyclopentane.It was further agreed that OORG Production Sector First Peer, Mr. Brian Joyner, would lead the planningeffort and that a draft report would be prepared for presentation at the Seventh OORG Meeting at WorldBank Headquarters on April 11, 1995.
It was agreed during the planning meeting that the draft report would address the following items:
* Essential technical specifications and safety, health and environmental (SHE) standards forhandling, transport, and storage of each of the relevant hydrocarbon products, mixtures orformulations - as defined by the principal user groups concerned, namely: refrigeration,foams and aerosols;
* Standard size/s of container/quantities of each hydrocarbon product which are typical foreach of the user groups;
$ Constraints on the availability of the relevant hydrocarbons within countries or regionsrelevant to the Bank's MP operations, including trade restrictions, transboundarytransport regulations, or other administrative barriers;
* Price of each hydrocarbon for standard size container/quantity, in terms of FOB at pointof production and/or storage, plus transport and delivery costs, and;
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Identification of sources of hydrocarbon supplies and their specific locations, includingcurrent or likely hydrocarbon product suppliers, preferably with affiliated agents, bycountry.
2. Maior Findings
Mr. Joyner began the presentation with a brief overview of the hydrocarbons under review (i.e.,propane, n-butane, iso-butane, n-pentane, iso-pentane, and cyclo-pentane) and their place in the Cl through C50hydrocarbon chain. For perspective, he noted that the total global consumption of these C3, C4 and C5hydrocarbons averages 221 m telyr which is less than a third of the total amount of all hydrocarbons consumedin a single day, i.e., 737m te/day. Furthermore, the LPG portion of this consumption is overwhelmingly used asfuel (99 percent), while only 1 percent is consumed in aerosols and a scant 0.01 percent is used in refrigeration.Indeed, if all of the world's refrigeration were converted to hydrocarbons today, that portion of total LPGconsumption would still only constitute around 0.1 percent of the total. Clearly, then, market conditions world-wide are such that whatever the usage, hydrocarbon prices in both the aerosol and refrigeration sectors arereceived prices in the first instance and consumption volumes are too low to yield economies of scale inproduction. Nonetheless, hydrocarbons are certainly available in the developing country world - in bulk and ata price. Price may vary greatly, however, as a function of transportation logistics, packaging, storage and safetyand these are different for each sub-sector.
In the case of both aerosols and foams, shipment in bulk tanks is feasible either to a central point ordirect to major users. Refrigerant supplies, however, will almost certainly require local repackaging into smallcylinders. Aerosol grade and/or refrigerant hydrocarbon supply at the national level depends upon the localavailability and quality. Local purification, if necessary, is only viable in a few of the largest developingcountries. The various pentanes may be available from local refinery streams but will depend upon wellheadquality and/or the availability of ethylene cracker/isomerisation units, as also upon the size of the market.
In some cases, region-oriented separation and purification plants might be justified to serve severalcountries in the Latin America and Asia regions. Depending upon the specific requirements, a typical plantproducing anywhere from 10 to 20k te/yr would cost in the range of $3 - 4 million. However, the technology iswell known and established and subject only to relevant conmmercial agreements and meeting safety standards.
The basic question to be answered in each sector in any country is how developed is the potential userdemand and is the associated "market pull" sufficient to promote and support such purification investments.
In most cases, therefore, user sector projects should be given fist priority for Multilateral Fundfinancing as a first step towards creating the necessary demand for indigenous supply. Whether on a national orregional basis, aerosol hydrocarbon supply projects should receive first priority, with refrigerant grade supplyconsidered as a possible extension of aerosol supply and only after undertaking a full safety evaluation of theprospect. Pentane supply for the foams sector cannot be justified at the present time, however this perspectivecould change in future should the building and construction foams industry also adopt hydrocarbons.
Subsequent discussion during the OORG Meeting emphasized the fact that decisions surrounding theadoption of hydrocarbon options in Article 5 countries should be taken at the national rather than the enterpriselevel and that refrigerant grade hydrocarbon specifications are still in a state of flux at the present timne.
3. Hydrocarbons Study Renort
The OORG Production Sector "Hydrocarbon Study Report" is presented in Appendix I of thisreport.
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APPENDIXI
OORGPRODUCTION WORKING GROUP
HYDROCARBONS STUDY REPORT
April 1995
by
Brian D. JoynerGregory CollinsMichael Harris
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Background to use of Hydrocarbons (HCs) in Replacement ofCFCs and HCFCs.
Aerosol
HCs have been used in certain types of aerosol products for at least 30 years, but were generally limitedto products where the major part of the formulation was water. In this way the potential flammability hazardof HCs was reduced. There was always a benefit in using HCs in that the lower density meant that less weightwas needed to fill the volume of the aerosol can. However, many types of aerosol product were based onflammable solvents. These could be made non-flammable with CFC propellants, but obviously not with HCs.Moves against CFCs, starting in the late 1970s, forced a re-consideration of HCs. Different types of solvent
system, new designs of valve and other technical developments have enabled virtually all types of aerosolproduct to be successfully reformulated on HC propellants.
Foam
For the purposes of this study we are considering only closed-cell polyurethane foam used for thermalinsulation. Typical applications are refrigerators, freezers, insulated road vehicles and building panels. In allcases the polyurethane foam adheres to the inner and outer surfaces to provide a rigid, thermally insulatingsandwich construction. The chemistry of the polyoVisocyanate reaction is strongly exothermic and the use of avolatile liquid, which can be evaporated by that heat of reaction, turns the liquid reactants into a foam whichbecomes rigid as it cools. The evaporation of the liquid helps to remove some of the heat, and the vapourremains trapped in the closed cells of the foam.
CFC,, was chosen initially for this application because it was easily evaporated, non-flammable,virtually non-toxic and provided an excellent insulation foam. The phasing out of CFCs, and eventually ofHCFCs, coupled with a German initiative for zero - ODP, halogen - free systems, focused attention onhydrocarbons. The pentanes, coupled with changes in foam chemical formulations, have been found to giveacceptable foam products.
Refriseration
CFCs were developed from 1930 onwards as refrigerants for domestic appliances, and spread into alltypes of refrigeration over the next 60 years. Throughout this period propane and isobutane have been knownto be efficient refrigerants, but flammability has restricted use to a very few, specialized, areas. The search forreplacements for CFCs has stimulated a review of all types of refrigerant materials, and HCs have emerged inEurope as viable candidates for domestic refrigerators and freezers, where small, hermetically-sealed,compressors are used. This view is not shared by all manufacturers in Europe, while manufacturers in the USAare at a very preliminary evaluation stage. Different technical and economic considerations may well apply forlarger compressors, or for non-hermetic systems, and the role of HC refrigerants must be viewed as in a veryearly stage of development.
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THE WORLD BANKOORG - PRODUCTION SECTOR
HYDROCARBONS STUDY REPORT - FINAL DRAFr
Overview
The information presented in this report is based on a disappointingly small response to thequestionnaire sent to hydrocarbon suppliers. A total mailing of 19 has resulted in only 9 responses (3 USA, 6Europe).
There is some evidence that hydrocarbon suppliers are positioning themselves to handle an anticipateddemand for hydrocarbons around the world. One producer, known to be operational on a world basis, declinedto participate in our study "for commercial reasons".
Price is a significant factor. Potential users, particularly in the aerosol industry, tend to regard hydrocarbonsas commodities (cf. fuel gases) whereas the reality is that the stringent user specifications require a chemicalspecialty price structure.
Europe is ahead of the USA in the use of hydrocarbons as urethane foamn blowing agents and as refrigerants.The USA led the switch to hydrocarbons in aerosols by several years, but technology in Europe has now caughtup.
In principle, both Europe and the USA are able to supply to all the countries on the World Bank list, althoughthe logistics of maintaining a steady availability using ISO tanks could be a real problem.
All of the hydrocarbons covered by this study are in ample supply in Europe and the USA, but availabilityelsewhere is believed to be problematic. There is a perceived potential shortage of isobutane at the distributorlevel. Producers state that this is really a price/purity situation, with ample isobutane "in the pipeline".
Purification technology is available as a package, coupled if necessary with storage, handling and packagingexpertise. Given agreed financial arrangements this could be made available to any country where suitable"raw" hydrocarbon streams are available. Using developed country economic criteria, the viability of ahydrocarbons purification project in any single country other than China trust be very doubtful. If multi -country arrangements could be agreed then projects in the Asia/Pacific and Latin America regions may qualify.
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Scone
Boiling Point Applicationor Range
°C
Propane CH3 - CH2 - CH3 42.1 A R
n - Butane CH3 - CH2 - CH2 - CH3 -0.5 A R
iso-Butane CH3 - CH-CH3 -11.7 A RI
CH3
n-Pentane CH3- CH2- CH2- CHR2- CH3 98-101 F
iso-Pentane CH3 - CH - CH2 - CH3 82-87 F
CH3
cyclo-Pentane CH2
CH2 CH2 120-133 F
CH2 --- CH2
Flammability
Flash Point Flammability Limits°C Vol. percent in Air
Propane < -100 1.8 -9.5
n - Butane <-70 1.4- 8.5
iso - Butane < - 80 1.4- 8.5
n - Pentane <-40 1.3 -7.6
iso -Pentane <-60 1.4 - 7.8
cyclo-Pentane <-40 1.4 - 8.0
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CONCLUSIONS
I General
1.1 The ODS uses considered in this report are:
* aerosol propellants* working fluids in refrigeration and air-conditioning* blowing of closed-cell insulating foam.
1.2 The hydrocarbons relevant to these applications are:
* C3 and C4 hydrocarbons (propane; n-butane and iso-butane) for aerosol and refrigeration use.These have boiling points well below normal ambient temperatures and are thus handled ashighly flammable liquefied compressed gases. Provision must be made for handling atconsiderable pressures.
* C5 hydrocarbons (n-pentane, iso-pentane, and cyclopentane) for foam blowing. These haveboiling points above normal ambient temperatures and are thus handled as highly flammablevolatile solvents. Storage, distribution and handling are significantly cheaper than for thelower boiling hydrocarbons and provision need only be made for modest over-pressures, e.g.at high ambient temperatures.
1.3 Whether these hydrocarbons are possible, practical, or environmentally the most appropriate,choices as substitutes for CFCs vis-a-vis other available replacements is a matter for the OORG userindustry sector groups and is not addressed here. Nothing in this report should be seen as anendorsement or disapproval of hydrocarbons or of any other substance or technology as areplacement for CFCs.
1.4 All of the relevant hydrocarbons are available in appropriate qualities in the developed world and, atleast by importation, in the LDCs - at least in bulk and at a price. The issues relate not toavailability per se but to logistics, packaging, storage and safety; and the consequential effects onprice. In turn, these considerations impinge upon the 0 balance between supply in LDCs via importsfrom the developed world, or by means of indigenous production of the requisite qualities andblends. In some cases only importation can currently provide the necessary products - but this maynevertheless be easier and cheaper than indigenous supply. This report does not consider thepolitics of indigenous supply vs. importation - only the practicality and the economics.
1.5 Most large petroleum and petrochemical companies have access to C3, C4 and C5 streams that theycould upgrade. Whether they choose to do so is a question of market economics, i.e., the volumesand prices available. In most cases, at today's state of use technology development, the markets aredriven by fuel and chemical feedstock uses both as to price and availability. This situation isunlikely to change.
1.6 If an indigenous supply capability is to be created, the requisite technology for purification(distillation and/or molecular sieve drying and deodorisation etc.), blending, packaging, storage anddistribution is well-known and readily available. However, indigenous sourcing may prove to be avery costly option (relative to importation) for all but the largest of the LDC markets, especially forthose products required only in small to moderate volume. UACs are then likely to becorrespondingly high. Handling these highly flammable liquids and gases, which form flammableand explosive mixtures with air,' entails significant costs if safety standards are to match those in thedeveloped world. Not unreasonably few, if any, potential technology providers will be willing tooperate to a lower standard in the developing world than in their own countries.
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1.7 In some cases (see below) there may be a case for regional purification facilities where nationalfacilities are grossly uneconomic. This could represent a compromise between importation andnational indigenous production by providing better economies of scale. Such cases, however, arelikely to be limited and unlikely to be found outside of the aerosol sector in the near future at least.
1.8 In many applications the relevant hydrocarbon products are blends. This will have an inevitableeffect on price as economies of scale are somewhat lost in the move to a variety of blended productsin smaller volumes. Market requirements may also differ geographically - especially in the aerosolindustry.
1.9 Although there is only limited toxicology data (and no long-term test data) available onhydrocarbons, most of them are unlikely to raise significant toxicology issues per se. The chiefexception is cyclopentane on which there is currently almost no health information available -although studies are now under way. However, the most likely impurities in the hydrocarbons arearomatic hydrocarbons (e.g. benzene, a known human carcinogen), higher alkanes (e.g. n-hexane,aknown human neurotixin) and alkenes. For this reason it is essential that purity specificationswhich maintain these toxic impurities at acceptably low levels are adhered to. Inevitably this willreflect in the price of products of safe and appropriate quality.
1.10 The volumes of hydrocarbons required as CFC substitutes are trivial compared with the world tradein the relevant hydrocarbons or hydrocarbon streams. Even aerosol use, by far the largest relevantuse in the developed world, represents only about 1 percent of the tonnage of C3 and C4
hydrocarbons in commerce. Foam use of n- and iso-pentane is also a minor proportion of thecommecial supply; cyclopentane is a special case as there has been little other commercial use todate. Refrigeration use of C3 and C4 hydrocarbons is currently extremely small as fraction of formerCFC use. Even if all refrigeration and air conditioning use of CFCs were converted to hydrocarbonsthe quantities of hydrocarbons involved would be minor compared with aerosol use, and wouldremain at less than 0.1 percent of the tonnage in commerce. Under these conditions, the prices of allof the relevant hydrocarbons (except perhaps cyclopentane) will be driven by the market prices forunrelated uses (primarily as fuels and/or chemical feedstocks), marked up for the small volumes andspecial qualities and blends required.
1.11 In general, for the reasons outlined above, the price of hydrocarbons will remain relatively high -certainly far higher than world prices for unblended and unprocessed hydrocarbons or hydrocarbonstreams in bulk. This is particularly true for the higher vapour pressure products (C3 and C4), and/orwhere the market for a particular product or blend is small (because of the application, or because ofthe size of the national market). Specialty hydrocarbons will in practice be priced competitivelywith other CFC alternatives; only the largest users are likely to enjoy bulk supply prices that showany significant advantage.
1.12 In all cases, the price of the requisite hydrocarbons, and the justification for investment inindigenous supply or beneficiation facilities, will be driven.
(a) by the overall supply/demand characteristics for the hydrocarbon streams in question -which is outside the control of the funding agencies, and/or
(b) the size of the specific ODS-replacement market for the particular blends or products ofrequisite purity.
As supplies of the hydrocarbons will always be available at the prevailing marketprice - even inLDCs - it will almost always be more cost-effective for the funding agencies to first fund the end-useprojects to create market pull.
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1.13 Where investment is by exception to be considered in hydrocarbon supplies, then having regard tothe relative volumes, and the relative stage of development of the enduse technologies forhydrocarbons, there is a very clear prioritization for World Bank funding, viz.
First: aerosol supplies: volumes are relatively large, the technology of use well-establishedfor over a decade, and the UACs of investment either attractively low or evennegative (and thus a candidate for soft loans).
Second:foam blowing supplies: volumes small to moderate, the technology of use relatively new(but already rather well-established where an expert polyol technology partnerexists), and the UACs for investment are in a reasonable mid-range.
Last: refrigeration supplies: volumes very small (and will remain so relative to other ODSuses even if substitution were total), the technology of use very new and not yetmuch accepted outside of Europe, and the UACs very high compared with otheroptions for ODS reduction in the same industry. In particular there is an absoluterequirement for emissions reduction before hydrocarbons can be used withoutdanger, and this essential prerequisite technology change (which will be beneficialwhichever refrigerant is chosen) carries an attractively low UAC and is a far betteruse of funds for the LDC refrigeration sector. Investment for local provision ofaerosol grades can also be a first step towards provision of refrigeration grades.
2 Aerosol Grades of Hydrocarbons
2.1 Aerosol applications require blends of C3 (propane) and C4 (n-butane, iso-butane) hydrocarbons atrather high levels of purity - especially with regard to odour. These are supplied as liquefiedcompressed gases. As a result, storage and distribution costs will be rather high, reflecting thesafety requirements inherent in the physical properties of the products. In addition, purity andblending constraints, as well as the fact that aerosol use is only a negligible fraction of thecommercial propane/butane market, will tend to keep prices well above those for unpurified bulkproduct.
2.2 At the appropriate qualities for aerosol use, there are unlikely to be specific toxicologicalconsiderations. The chief SHE considerations are those associated with the flammability of thegases and their ability to form explosive mixtures with air.
2.3 Basic feedstock for aerosol use may be available at the well-head (as natural gas liquid, NLG orLPG) or from petroleum refineries. Purification will generally require distillation to give separateproducts of minimum 95 percent purity, and will certainly involve drying and purification to removewater and odoriferous impurities (e.g. sulphur compounds and alkenes). Blending is required toprovide the commercial range of hydrocarbon aerosol propellants (HAPs) of appropriate vapourpressure characteristics Dedicated distillation facilities should normally be provided by a refinerysite or - in larger user countries - by an intermediary supplier of industrial gases. Only one or twosuch facilities exist even in aerosol markets as large as the USA or the UK.
2.4 Only the larger user enterprises will handle sufficient volume to provide a practical and economicbasis for in-house purification (e.g. molecular sieve treatment). Only these, and maybe somemedium-size users will economically justify in-house blending. The smaller aerosol filling facilitieswill need to purchase purified blends. Because CFCs are non-flammable and generally much easier
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to handle, some smaller users will become uneconomic and a measure of industrial rationalisation isto be expected.
2.5 In the LDCs, only the very largest are likely to require domestic distillation capacity at the nationallevel. There may in addition be a case for regional distillation capacity e.g. in South-East Asia orLatin America. At the national level, a handful of other relatively large LDCs might have aneconomic case for a national purification and blending capability. Apart from these options,importation of appropriate product may well remain the lowest UAC (i.e. most cost-effective) optionfor phasing out CFCs in the aerosol sector.
2.6 In the developed world, the replacement of CFCs by HAPs has proved economically attractive,although initial capital investment to establish appropriate safety measures, and to make appropriateblended products available, has been significant. The replacement HAPs are no more expensive (ona weight basis) than CFCs and, because of the lower liquid densities, only about half the weight ofpropellant is needed. However, potential corrosion problems and the need for greater amounts ofodour masking agents (generally perfumes, which are expensive) can diminish this apparent cost-saving to a level at which it is not always perceived as attractive enough under developing worldconditions to drive the initial capital investment.
2.7 In the largest LDCs, given a national initiative to replace CFCs, it is likely that UACs could besimilar to those in the developed world. In the smaller LDCs, the lack of economies of scale forindigenous supply may increase UACs significantly and make importation the most attractivelowest UAC) option. Regional purification projects may help in this regard.
2.8 Whether UACs are low and positive, or actually negative, will depend critically on the time periodover which the project economics are calculated. Use of normal commercial project lifetimes of 2-5years is likely to yield negative UACs in many cases. Use of a shorter project lifespan (e.g. oneyear) may result in low positive UACs. Where UACs are actually negative it may be difficult tojustify grants from the MLF - but soft loans may be appropriate if it is the actual iniial availability ofcapital tht is at issue.
3 Refrigeration and Air Conditioning Grades of Hydrocarbons
3.1 Refrigeration and air conditioning applications are similar to aerosol uses in requiring C3 (propane)and C4 (n-butane, iso-butane) hydrocarbons, or their blends, at very high levels of purity - althoughodour is less critical than for many aerosol uses. Cost/price considerations are thus similar - exceptinasmuch as the very much smaller volumes involved place a further upward pressure on deliveredprices.
3.2 At the appropriate qualities for refrigeration use, there are unlikely to be specific toxicologicalconsiderations. The chief SHE considerations are those associated with the flammability of thegases and their ability to form explosive mixtures with air.
3.3 The volumes of hydrocarbons required as CFC substitutes are currently very small indeed, especiallyin the LDCs, as a fraction of the total requirement for ODS replacements. Even these volumes arean almost negligible fraction of the market for commercial propane and butanes. Prices will bedetermined by overall demand for C3 and C4 hydrocarbons, modulated by aerosol industry demand -especially where qualities are similar. It is not yet known whether purity requirements forrefrigeration grades will fall from the present typical 99 percent+ level to the 95 percent+ levelsmore associated with aerosol use. If this happens, refrigeration hydrocarbon prices could drop fromtheir present extremely high levels to levels similar to those of HAPs but still far above that of the
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bulk products. Nevertheless, in the small hermetic equipment likely to use hydrocarbons (e.g.domestic appliances) the refrigerant cost is not a significant part of the cost of the final fabricatedproduct.
3.4 No refrigeration industry user in the foreseeable future is likely to require product in volumesrequiring in-house beneficiation. In future, the market will either be supplied with aerosol gradeproduct or, where higher purities remain necessary, by specialty gas suppliers who will handle thepurification and packaging issues. Even the largest refrigeration industry users are unlikely torequire more than bulk storage facilities appropriate for flammable liquefied compressed gases.
3.5 No LDC beneficiation or supply capability is likely to be needed beyond that required for the fargreater volumes of aerosol use - even if there were to be near total replacement of CFCs byhydrocarbons in refrigeration. Importation will normally remain the only remotely economic sourceof supply wherever indigenous aerosol beneficiation facilities either do not exist or do not provideadequate qualities of product.
3.6 Although hydrocarbons have long been used as refrigerants, this has been restricted in recentdecades to certain types of large industrial equipment on chemical plants and petroleum refinerieswhere the necessary safety and handling conditions are intrinsic to the existing process operations.The historical use of hydrocarbons in smaller commercial equipment (prior to the development ofthe CFCs to meet the market demand for a non-flammable and non-explosive alternative) was notunder conditions which would meet present-day safety standards.
3.7 The modern market for hydrocarbons in small hermetic equipment (e.g. domestic refrigerators)currently exists to any significant degree only in Continental Western Europe. It is, at the time ofwriting, quite uncertain as to the extent to which this technology will find wider market acceptancegeographically or as to end-use. At this stage of technological development it would beinappropriate, if not unethical, to use the LDCs as "guinea-pigs" for technology which is only 1-2years old even in the most developed markets and applications and whose acceptance is far fromuniversal. To the extent that LDCs wish to evaluate this technology it can certainly be done byusing imported products without any constraint on technology development. If the LDC markets doat some future date develop to an extent requiring larger volumes it is almost certain that the supplyrequirements can be met at marginal additional cost from the arrangements which by then should bein place to satisfy the larger volume aerosol requirements.
3.8 Although the extent to which the use of hydrocarbons as CFC replacements will develop in therefrigeration industry is uncertain, it is clear that, for safety reasons, and to satisfy regulatoryconstraints, the technology of use, maintenance and disposal will need to approach a zero emissionsstandard. These engineering standards will of course also be highly beneficial whatever refrigerantis chosen, e.g. in minimizing toxicity risks with ammonia, or the small global warming impact fromHFCs. As near zero emissions is a clear advantage for all refrigeration technologies, and an absoluteprerequisite for hydrocarbon use in refrigeration, this is the clear first priority. As the UACs foremission reduction are attractively low, investment in this area is a high priority - and will in anycase be a necessary prerequisite before safe investment can be made in any wider use ofhydrocarbons in this area.
3.9 By a similar argument, at the end-user level projects financing conversion of appliancemanufacturing facilities to use hydrocarbons for foamblowing (e.g. flame proofing of equipmentand buildings) will by the same token prepare the ground for the use of hydrocarbons in refrigerationif this is later deemed appropriate. Refrigeration conversion projects perse are unlikely to needseparate financing.
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4 Foam Blowing Grades of Hydrocarbons
4.1 The blowing of insulating polyurethane foams with hydrocarbons requires supplies of C5hydrocarbon streams. Originally the technology developed around cyclopentane. More recently, theuse of n-pentane and iso-pentane or pentane blends has developed primarily for cost-saving reasons.
4.2 The pentanes are volatile flammable solvents with boiling points well above normal ambienttemperature. As such they are considerably easier to handle than the lower boiling C3 and C4hydrocarbons required by the aerosol and refrigeration industries. Accordingly the cost of therequisite products is at a smaller premium over bulk supplies, even for the purer grades and blendsthat the industry specifies.
4.3 The evidence to date is that, so long as toxic impurities are kept to an acceptable minimal level, thepurity requirements of the foam blowing industry are considerably less demanding than for theaerosol and refrigeration industries. Low odour levels are important where there is any possibility ofcontact with, or migration into, foodstuffs. However, the isomeric purity of mixtures seems lesscritical. Importantly there is also little evidence that the major impurity (2,2-dimethylbutane) incommercial 70 percent cyclopentane is an operational concern.
4.4 Toxicology is an area that may require further investigation in blends using cyclopentane (with orwithout the 2,2-dimethylbutane congener). Tests are under way and some caution may be necessaryuntil some health data is available.
4.5 Volume requirements are currently estimated as intermediate between those of the aerosol industrylarge) and the refrigeration industry (small). Volumes could become a lot larger if there is significantuptake in the building and construction industry. In this area, however, evaluation is still at a veryearly stage. Nevertheless, under all scenarios, the volumes of n- and iso-pentane involved are notlarge enough to affect market pricing significantly. As there are few other uses for cyclopentane,prices here may be far more dependent on foam industry offtake - but are intrinsically so muchhigher than those for n- and isopentane that the latter products are likely to dominate in the longerterm except perhaps in the highest quality foams (which will be priced accordingly). In general it islikely that the choice of polyols and formulation, dependent on the expertise of a polyol technologysupplier, will have a far greater influence on foam cost than prices of the pentane isomers used.
4.6 Pentane supplies may stem from the well-head (e.g. much cyclopentane in the USA), from refinerystreams (e.g. n- and iso-pentane generally), or be "synthetic" (e.g. much cyclopentane in Europe).The description "synthetic" as applied to cyclopentane in this context refers to the hydrogenation ofcyclopentadiene derived from ethylene crackers and isomerisation units.
4.7 There is less evidence of local supply constraints in the LDCs for C5 hydrocarbons for foam blowingthan for the C3 and C4 hydrocarbons for other uses. This is almost certainly because theattractiveness of the use technology has made the users willing to pay the market prices for importedmaterial (where local supplies are unavailable), given that the cost of the foam blowing agent is aminor proportion of the total cost of the fabricated products (e.g. a domestic appliance). Thissituation might be different for building and construction industry uses where blowing agent costsare more critical.
4.8 The UACs for projects to facilitate the local supply of C5 hydrocarbons for the polyurethane foamblowing industry are unlikely to be as attractive as those for the conversion of foam blowing lines tothe use of C5 hydrocarbons - even where the latter reflect the full current market prices of importedpentanes. By financing the end use of pentane blowing agents in appropriate cases as approved by
13
the relevant OORG sector group the market for the appropriate grades of products will be increasedand the case for local investment in on-shore supply enhanced.
14
RECOMMENDATIONS
1. There is little evidence that hydrocarbons are simply not available - at the market price. Accordinglythe most effective approach to improving availability will usually be "market pull", i.e., to create thedemand. Often this will then automatically stimulate the supply of the appropriate products atacceptable prices. Therefore, investment in facilities to improve the supply of hydrocarbons as ODSreplacements in LDCs will usually be less cost-effective and have higher UACs than investments toenhance the use of hydrocarbons. End-user projects should normally receive higher priority forfunds.
2. There may be exceptions to the foregoing where importation is inconsistent with the nationaleconomic and industrial policy of the LDC concerned. Such exceptions will need to be decided ona political basis by the Executive Committee vis-a-vis other calls upon the Multilateral Fund.
3. There may be exceptional cases, eg in the largest LDCs or on a regional basis, where funding agencyinvestment in hydrocarbon supply projects is justifiable. At present it seems probable that there willbe a few such cases in the case of supplies to the aerosol industry, in particular the support ofregional facilities in South East Asia and Latin America. The UACs of these projects will needcritical examination as although they are likely to be low (and therefore attractive) they may actuallybe negative - in which case soft loans may be more appropriate than outright funding.
4. It is possible that there may be in the future one or two further suitable projects relating to supply ofpentanes to the foam blowing industry. However, at present it appears that investment in end-userprojects carries much more attractive UACs and should be given priority. This recommendationcould change if hydrocarbon foam blowing technology extends significantly into the building andconstruction industry.
5. There is no case in the foreseeable future for supply side investment in hydrocarbons for therefrigeration industry. This is because (a) the volumes will be very small - even if hydrocarbonsextensively replace CFCs in refrigeration - relative to aerosol industry demands for similar grades.Thus supplies will largely be covered by arrangements made for the more clear-cut case of aerosolpropellant demand, and (b) near-zero emissions is a necessary safety and regulatory prerequisite forsafe hydrocarbon use in refrigeration, carries a far lower UAC, and does not constrain the userindustry to the use of any one particular type of refrigerant. Emissions reduction projects thereforehave a higher priority call on finite funds.
6. The use of hydrocarbons as ODS replacements is a relatively new development outside of aerosolpropellant use and there is therefore a need to maintain a watching brief on the relevant markets toensure that no inappropriate constraints on supplies in LDCs exist. There is also a need to maintainmarket intelligence on the development of the relevant end-use technologies and their hydrocarbonmaterials requirements to ensure that supplies are adequate. Overall the ODS replacement field israpidly developing. For this reasons, the Production Sector Hydrocarbon Working Group should bemaintained in existence on a holding basis, and the topic should remain on the agenda forsubsequent OORG meetings.
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CFC Replacement by Hydrocarbons
Aerosol
Propane/butane/isobutane mixtures plus isobutane alone.
Odour is the most critical specification parameter. Without the use of a qualified "Odour Panel" it isimpossible to quantify and measure. Developing and maintaining a trained panel of experts who can detectsubtle and subjective malodours is most difficult. In the fragrance industry, the perfunmer is the key to thebusiness, while in the general aerosol business the establishment of a "Best in Class" non-malodour panel is thekey to success. A typical specification will read "as agreed between customer and supplier", with the customerhaving the right to reject a delivery before off-loading if a sample is found to have an unacceptable odour.
Sulphur compounds are one cause of unacceptable odour, and specification limits are usually at theparts per million level. Unsaturates and water also feature in supplier specifications, examples of which aregiven in Appendix 1.
A "typical" specification could be:
Purity, wt. percent (min) 95.0Odour "Free of Odour" or "As Agreed with Customer"Uri .turated Hydrocarbons mol. percent (max) 2.0
-.l phur, ppm (max) 1.0Water, ppm (max) 10.0
Hydrocarbon propellants are normally referred to by the vapour pressure delivered at a standardtemperature, usually 210 C (70 °F), as shown in Table 1.
Table 1
Hydrocarbon Propellant Vapour Pressures
Name Vapour Pressure Typical Composition percentpsig @ 70OF Propane iso-Butane n-Butane
AP17 15-19 - - min. 95AP30 28-32 11 29 60AP31 29-33 - miin. 95AP40 38-42 22 24 54AP48 46-50 31 23 46AP70 68-72 55 15 30AP107* 105-109 min. 95 3 2
*Suppliers variously call this 105, 107 or 108
Although suppliers offer the range of blends it is common for major aerosol fillers to purchase tank carlots (minimum 10 tonnes) of the nominally-pure compounds and prepare their own blends. One major UK
16
contract filler installed a molecular sieve deodorising facility some years ago and purchases "pure" butane andpropane ex - refinery for final polishing and blending. Purchases of around 3,000 tonnes p.a. are primarily forown use but small amounts (10 tonne lots) are sold to smaller fillers.
See Appendix la for typical purchasing specifications.
Small containers (nominally 50 kg in the UK) are much less common, generally reserved for trial lotsof special blends.
Bulk tank prices offered in Europe are $550 to $650 per tonne, FOB.
A larger range of small containers (1 to 125 US gallon cylinders) is offered in the USA, but the pricingstructure makes bulk deliveries far preferable, as Table 2 shows:
Table 2
US Propellant Prices$/US gallon $/kg.
Bulk ex works 0.90 0.45
125 gall. delivered US 6.20 3.1050 gall. delivered US 11.70 5.855 gall. delivered US 24.00 12.00
Note: These figures are averaged and not strictly comparable between bulk and cylinders, but the point isclear. In fact it seems likely that, small containers are used in the USA only for sample lots.
Foam
n-Pentane, iso-Pentane, Cyclopentane; and mixtures.
Note: Data from only one supplier and one industry expert for n- and iso-pentanes; three suppliers andthe expert for cyclopentane. Purity, in terms of title compound, is min. 95 percent for n- andiso-pentane.
For cyclopentane, purity ranges from 70 percent to 95 percent and it appears that both are equallyacceptable in terms of foam quality.
Limits for Benzene and n/iso-Hexane are set at low ppm levels (typically 1 ppm for Benzene, 10 ppmfor n - Hexane)
In respect of other quality criteria it would appear that "ordinary" or "commodity" grades areacceptable. Actual supplier specifications are detailed in Appendix 2.
A "typical" specification could be:
Purity, wt. percent (min) 95.0
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Note: Cyclopentane in USA 75.0main impurities 2,2 - dimethylbutane and n-pentane
Acidity NeutralAromatics, individually named, ppm (max) 2 to 10Sulphur, ppm (max) 10.0Non-Volatile Residue, ppm (max) 10.0
n- and iso-pentanes are favoured for construction panels, cyclopentane for refrigerators, freezers anddisplay units.
Delivery is by bulk "solvent-type" tanker or in 200 litre drums (barrels). Bulk supply is stronglyrecommended on grounds of safety (possibility of careless handling of drums of highly flammable liquids,explosion risk from residual vapour in empty drums).
The bulk tank should be cited outside the factory walls, preferably underground and with Nitrogenblanketing, but close to minimise pipe runs.
Price indications cover too wide a range for averaging to be appropriate:
n/iso pentane in bulk US $ 465/te FOBEurope $ 1,300/te Delivered in Europe
Cyclopentane in bulk US $1,177/te FOBEurope $1,755/te FOBEurope $3,200/te C&F
Asia/S. Americain drums (FCL) Europe $2,400/te FOB
It is clear that n- and iso-pentane prices are significantly lower, less than half of those of cyclopentane.Some domestic appliance manufacturers are now satisfactorily using blends of n/iso-pentanes withcyclopentane, and cost-saving is at least part of the reason.
Europe is far in the lead in utilizing hydrocarbon blowing agents in rigid foams, with the USA still onlyat the trials stage. There is little or no interest from US equipment suppliers, who reportedly have no test ordemonstration facilities themselves.
This situation is at least partially due to anticipation of problems with US Fire Marshals and withUnderwriters Laboratory Building Code inspectors.
Refriaeration
Primarily iso-Butane, with some Propane.
The refrigeration sector, led by compressor manufacturers, demands the tightest "technical"specification. For example, iso-butane is required to be at least 99.5 percent pure (in terms of title compound)by some compressor manufacturers despite demonstrable evidence that the presence of 1 or 2 percent of n-butane or propane makes no significant difference in refrigeration properties. This emphasis on title compoundpurity is really a way of ensuring that levels of undesirable impurities (unsaturates, sulphur compounds) arekept down to trace amounts.
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The justification for such a stringent specification is being questioned by some in the industry, butcertain equipment manufacturers are still adamant that it is correct.
The major UK supplier of hydrocarbon refrigerants has just introduced a range of blends (propane, n-butane, iso-butane) designed to match the refrigeration properties of R 12, R 22 and R 502. See Appendix 3.
Blends introduce a phenomenon known as "temperature glide," arising from the differing boiling pointsof the components. This can introduce difficulties but can also be turned to advantage in some types ofequipment.
Note It cannot be over - emphasised that the use of hydrocarbons in general purpose refrigeration is in it'sinfancy, is essentially limited to domestic appliances so far, and with the only serious use being inGermany. Significantly, hydrocarbons are not permitted in the major US refrigeration sector of MobileAir Conditioning.
Refrigerant supplier specifications are listed in Appendix 4.
A "typical" specification could be:
Propane or IsobutanePurity, wt. percent (min) 99.5 (moving towards 98.0)Unsaturates, ppm (max) 100Sulphur, ppm (max) 5.0Water, ppm (max) 10.0Non-condensibles, percent in vapour (max) 1.5Acidity, ppm (max) 100Non-volatile, residue, ppm (max) 50
Bulk delivery of hydrocarbon refrigerations will only ever be appropriate for major manufacturers offactory-charged equipment (primarily domestic refrigerators and freezers, and other hermetically-sealed items).For smaller manufacturers it is doubtful whether the costs of compliance with Health and Safety regulationsgoverning the storage tanks and pipework installation can be justified.
Cylinders, of capacity ranging from 5 kg to 50 kg, are the only practicable means of supply to therefrigeration service industry, and offer considerable handling and stock flexibility advantages even inmanufacturing situations. However, regulations governing the safe storage and transportation of flammablegas cylinders are rigorous, covering limits on quantities permitted indoors, free space around outdoor storage,permitted quantities in closed vans, etc. Extracts from the UK Regulations are shown in Appendix 5.
From the very sparse price information available so far it is clear that hydrocarbon refrigerants are notcheap. They are, in fact, comparable on a unit of use* basis to the price of CFCs or HFCs in any area wherethere is no artificial constraint such as a tax or levy. For example:
Hydrocarbon Blends(95 percent propane, propane/isobutane mixtures, 95 percent isobutane)
$/kgA single 6 kg cylinder 30 UK marketBulk shipment of cylinders in cages (closed container box not allowed) 20 FOB UKBulk tank containing 10 tonnes 15 FOB UK
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Isobutane. min. 99.5 uercent
No precise data were forthcoming, but general information is that there is little difference in pricebetween 95 percent and 99.5 percent isobutane.
Propane
$/kg99.5 percent Propane in small cylinders 20 to 33 German marketMin. 98.0 percent Refrigeration Gradein 10 tonne bulk tank 4.0 FOB USA
*The term "unit of use" takes account of the density difference between CFCs and Hydrocarbons.Refrigeration equipment requires a certain volume of refrigerant, and this volume of hydrocarbons typicallyweighs 50 percent to 60 percent less than the same volume of a CFC.
SUtDDIV:
After availability of refrigerant quality material, the primary requirement for a supplier is the ability tofill, handle and control large numbers of small cylinders. This is a major logistical exercise and must not beunder-emphasised in any potential venture. For example, the major UK supplier of hydrocarbon propellants iscurrently not prepared to consider any small container business.
Safety. Health and Environmental Issues
Safet
The hydrocarbons under consideration divide into two groups:*Propane and the Butanes Liquefied Gases, requiring pressure vessel storage*The Pentanes Volatile Liquids, with boiling points above ambient temperatureAll are flammable and can form explosive mixtures with air.
The Flash Points, Flammability Limits and appropriate Risk and Safety phrases applicable in Europeare given in Appendix 6.
Comprehensive Regulations and Codes of Practice exist for compressed gases, prepared and issued byGovernment Agencies and Trade Associations. It is not proposed to reproduce them in this report, simply toidentify their existence and to catalogue them. They can be readily accessed when needed.Some examples:
UK Aeencies
The Health and Safety Executive (HSE)The Liquefied Petroleum Gas Industry Technical Association (LPGITA)The Institute of Petroleum (IP)
20
Publications
HSE Booklet HS (G)34 The Storage of LPG at Fixed InstallationsHSE Booklet HS (R)21 A guide to the Control of Industrial Major Accident
Hazard (CIMAH) Regulations, 1984LPGITA Code of Practice Installation and Maintenance of Bulk LPG Storage at
Booklet No. 1 Consumer Premises.LPG Safety Code Part 9 of the Institute of Petroleum's Model Code of
Practice in the Petroleum Industry.
USA Agencies
The Department of Transportation (DOT)The National LP Gas AssociationThe National Fire Protection Association (NFPA)The Occupational Safety and Health Administration (OSHA)
Publications
US-DOT Regulations Governing Transportation of Hazardous Materials(49 CFR, Parts 100- 199, 1977)
National LP Gas Association, LP Gas Safety Handbook NFPA-58, Part 21 (1976)OSHA Storage and Handling of Liquefied Petroleum Gases (29 CFR 1910; 110, 1976Examples of such publications are shown in Appendix 7.
Additionally, there are the World Bank's own safety guidelines, currently being reviewed by ArtFitzgerald.
Health
Although they have not been subjected to detailed toxicology studies on the same lines as the HCFCand HFC substitutes for CFCs, there is no reason to suspect that exposure to propane and the butanes wouldpose any health hazard apart from narcosis and asphyxiation.
The same is broadly applicable to the pentanes although cyclopentane, which has only recently becomean "article of commerce," is the subject of some current studies.
Further information is to be sought on these, especially on the role of 2,2-dimethylbenzene in" 75percent" purity cyclopentane.
One of the reasons for tight purity specifications is the known toxicology of likely impurities (e.g.benzene, a carcinogen; n-hexane, a neurotoxin ).
Note: It could be appropriate to append examples of supplier Material Safety Data Sheets.
Environment
All of the hydrocarbons under consideration are classified as Volatile Organic Compounds (VOCs) andcould be subject to local regulations as atmospheric pollutants. This should be taken into account whendesigning ventilation and extraction systems for factory premises, niecessary for employee safety.
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The vapours of all the hydrocarbons under consideration are heavier than air, and fume extraction mustbe at low level. Particular care must be taken to avoid accumulation of vapour in enclosed, low - lying areas.
Specific User Issues under SHE
Aerosol
The actual injection of hydrocarbon propellants into aerosol cans (gassing) should be performed in aseparate area away from all other operations. Suppliers of aerosol filling equipment have ample expertise inthis area and can provide reliable guidance. The usual practice when converting from CFCs to hydrocarbons isto provide a totally separate room in which the propellant "gassing" operation is performed. This can be a self -contained unit within the factory, but is better as an extra unit, cited in the open outside the factory shell withconveyor track running out to, and back in from, this "gassing" unit. A further degree of sophistication in termsof safety is to have the "gassing" unit operated automatically by remote control so that there is no need for anyoperators to remain fulltime in that unit, but this is only practicable with efficient and reliable filling equipment.
Foam
Effective fume extraction is essential from all areas where hydrocarbons can be released into theatmosphere during mixing, foaming and curing stages of foam production.
Flameproofing, modifications to processing equipment, atmospheric monitoring/warning systems andenclosure of mixing operations to minimnise hydrocarbon vapour release are all key parameters. As with aerosolfilling, equipment suppliers should be approached for their experienced guidance.
Costs in the range $2 to 5 million have been quoted for the elimination of CFCs from domesticappliance manufacture at a production level of around 1 million units/year. This covered both refrigerant andfoam blowing, but probably at least 75 percent of the costs were associated with the foam area.
Refriaeration
Factory production situations are broadly similar between aerosol, foam and refrigeration applianceproduction. As with CFCs, refrigerants are known to be gases under pressure in their containers, and rigorousengineering and working practices can minimise the risk of leakage. The safe detection of leaks is moredifficult since many of the types of leak detector satisfactory for CFCs or HCFCs are unsuitable. Helium leakdetection is the best but is expensive, and extremely sensitive, necessitating a "clean" background atmosphere.Some types of electronic detection, and the use of oil - soluble fluorescent dyes, are other possibilities.
Appliance design or re-design is critical, to ensure that any possible points where leakage of refrigerantmight occur (e.g. pipework joints) are sited away from sources of electrical energy. Helium leak detection ismost usual in this area.
Design is also critical if the use of blends is being considered, in view of the temperature glide aspect.Some major equipment manufacturers are not willing to consider blends at present
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The primary area of concern is the refrigeration service industry, where personnel whose entire trainingand experience has been with non - flammable CFCs and HCFCs, need to be retrained in the safe workingpractices essential with hydrocarbons.
The primary supplier of HC refrigerants in the UK is now running a series of training coursesthroughout the country. As far as it can be achieved, they and their distributor are aiming to ensure that HCrefrigerants are not sold to anyone who can not show that they have been adequately trained.
Note: BDJ attended one of these courses on Monday 13 Feb. Extracts from the training notes relevant tosafety are attached as Appendix 8.
It is worth noting that, at this time, refrigeration appliances containing hydrocarbons fail to meet therequirements of some. National regulations or standards. For example, in both Germany and the UK,manufacturers are currently not complying with DIN or British Standard requirements. e.g. Appendix 9.
Revised drafts of such Standards have been published for public comment.
International Trade Restraints
The only problem identified so far is in regard to road transport across some European countries.There is a growing trend towards onerous regulations affecting carriage of flammable compressed gases. Theseregulations seemingly do not apply to LPG fuel gases, but the inconsistency in this seems to be lost on theregulatory agencies concerned!
Some examples of Regulations and Classification Codes are given in Appendix 10.
Developina Country Supply Possibilities
The over - riding factor in considering the potential availability of hydrocarbons for aerosol orrefrigeration use is that these markets are invariably miniscule alongside the use of LPG as fuel, and will remainso for the foreseeable future. To put the potential market volumes listed in Table 4 into perspective, a new UKpurification facility for Propane and Butane/Isobutane, commissioned about 5 years ago by a basic producer,has a capacity of 30,000 tonnes p.a. The total production capacity in the UK is in the order of 65,000 tonnesp.a.
A detailed account of the technology required to produce Propane and the Butanes for the aerosolmarket has already been prepared for another publication (Aerosol Conversion Technology Manual;commissioned by UNEP; awaiting publication) and extracts are reproduced as Appendix 11.
Production for refrigeration use would be exactly the same but would require either more rigorous , oran additional, distillation stage to attain the required 99.5 percent purity level.
The Pentanes are routine refinery distillation products following cracking of crude oil, although there isalso a chemical synthesis route for Cyclopentane. The presence of sulphur compounds (normally specified as 5or 10 ppm max) is not normally a problem, though somewhat dependant on the type of crude available, andodour is not usually a factor.
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Costs
Some indicative figures on capital and processing costs have been obtained:
USA
Distillation, and Deodorisation by means of Molecular Sieve treatment. Units installed on anoperating refinery site where all infrastructure, feedstock storage, safety measures, etc. are already in place.
Capacity 10,000 tonnes p.a.Capital cost ca. $3 millionOperating cost ca. 2 cents/kg.
UK
Deodorisation unit taking 95 percent and 98 percent purity feedstocks ex - refinery, complete withall "crude" and "product" storage tanks, tanker loading facilities, etc.
Capacity 20,000 tonnes p.a.Capital costs Mol. sieve columns (3 pairs) ca. $1.6 million
Total Package ca. $3.8 millionOperating cost Not provided at this stage
An attempt at costing potential production scenarios is given in Appendix 12.
Possible Develoning Country Sources
The following list is of possible sources of hydrocarbons identified of interest in this study. The keyelement identifying these possible sources is the type of crude oil distillation technology employed. Cracking isthe process for making molecules with 5 - 12 carbon atoms from larger molecules or the process for convertingsaturates like ethane or propane into ethylene or propylene. Steam or Thermal Cracking is used to produceolefins with some aromatics also being produced. Catalytic Cracking facilitates formation of branched chainand aromatic molecules while also producing C3 and C4 olefins as in Steam Cracking, but in lesser amounts andin more dilute streams. Isomerization is used to convert straight chain to branched chain compound. e.g. n-Butane to Isobutane. The following list (by World Bank countries of interest) identifies whereThermal/Catalytic Cracking and Isomerization capacity exists.
Whether or not the particular hydrocarbon streams and additional purification equipment are availableat the identified locations is not known, nor is the availability of hydrocracking known (hydrocracking gives thelowest levels of aromatics and unsaturates). This list is intended simply to indicate the most likely locations tofind the hydrocarbons of interest.
Algeria No catalytic or thermal cracking found.
Argentina Thermal/catalytic cracking units but noIsomerization found.
Esso SAPA Campana, GalvanYacimientos Petroliferos La Plata, Lujan de Cuyo, San LorenzoIsaura SA Bahia BlancaShell Buenos Aires
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BrazilPetroleo Basileiro SACubataso Sao Paulo
ChlePetrox SA TalcahuanoRefineria de Concon Concon
China No current information
EcuadorPetroecuador Esmeraldas
EgyptAmerya Oil Refining Co. Alexandria
lndiaBharat Petroleum CL Mahul, BombayBongaigaon Refinery & Petrochemical Ltd. Bongaigaon, AssamCochin Refineries Ltd. AmbalamugalIndian Oil CL Koyali, Gujarat
IndonesiaMusi South Sumatra
JordanJordan Petroleum Refinery Zerka
Malaysia No thermal/catalytic cracking
MexicoPetroleos Mexicanos Minatitlan
NigeriaKaduna Refinery & Petrochemical Co. KadunaPort Harcourt Refining Co. Alesa Eleme
PakistanNational Refinery Ltd. Korangi, Karachi
PhilippinesCaltex, Inc. BatangasPetron Corp. Limay, Bataan
Slovenia No current data
ThalandThai Oil CL. Sriracha
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Tunisia No thermal/catalytic cracking
TurkeyTurkish Petroleum Izmit
UruguayAncap La Teja, Montevideo
VenezuelaCorpoven El Palito, CaraboboLagoven Judibana, FalconMaravan Punta Cardon, Falcon
CFC/HC Conversion Benefits
Data on the pattern and volume of use of CFCs, in reference years ranging from 1992 to 1994, arepresented in Table 3. These data are taken from the Country Programme Summary Sheets held by theMontreal Protocol Multilateral Fund.
The figures are summarized and re-presented in Table 4 to show where the greatest ODP-savings areto be gained. This is not intended to suggest that projects in lower-consumption countries should receiveless favourable attention -- all savings are worth achieving provided the cost/benefit analysis is favourable.However, using the approximate factor of 50 percent by weight of Hydrocarbon in replacement of CFC, the"Hydrocarbon Equivalence" column in Table 4 indicates the scale of project that could currently be requiredin each country. It is clear that, unless there are unusual local factors, most of these would not be viable ona National basis.
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Table 3CONSUMPTION of CFC's
ODP Tonnes
Country Aerosol Foam Refrigeration Total Ref.Year
Algeria 559 650 754 1,963 1993
Argentina 173 1,484 2,078 3,735 1994
Brazil 255 1,950 5,748 7,953 1994
Chile 254 345 241 840 1992
China 8,600 17,773 12,869 39,242 1993
Ecuador 464 68 162 694 1992
Egypt 91 677 671 1,439 1992
India 1,100 1,576 1,990 4,666 1993
Indonesia 2,000 1,025 2,096 5,121 1994
Jordan 224 117 206 547 1993
Malaysia 253 415 1,720 2,388 1992
Mexico 993 1,629 4,796 7,418 1992
Philippines 5 417 1,217 1,639 1993
Thailand 475 1,532 3,292 5,299 1993
Turkey 999 1,454 651 3,104 1992
Uruguay 23 109 170 302 1993
Note: Data from the Global Aerosols Program indicate that in 1993 the Aerosol use of CFCs in Mexicohad dropped to 250 tonnes, and in Turkey to 10 tonnes. This probably indicates that hydrocarbonpropellants are already available in those countries.
27
Table 4
Consumption of CFCs*/HCs Equivalence #
Country CFCs Hydrocarbon Equivalence TonnesODP Tonnes Propane/Butanes Pentanes
China 39,242 10,700 8,900
Brazil 7,953 3,000 1,000Mexico 7,418 2,900 800Thailand 5,229 1,800 800Indonesia 5,121 2,100 500
India 4,666 1,500 800Argentina 3,735 1,150 750Turkey 3, 104 900 700Malaysia 2,388 1,000 200Algeria 1,963 700 300Philippines 1,639 600 200
Egypt 1,439 350 350
Chile 840 250 150Ecuador 694 300 50Jordan 547 250 50Uruguay 302 100 50
* The tonnages shown represent only consumption in the three areas of use under consideration in thisstudy.
# Using a very approximate density factor of 0.5
Note: The appendices to this report amount to about 100 pages of detail in order to reduce the bulkof the publication they are not reproduced in full. They are indexed below and are availableon request from OORG Administration.
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INDEX TO APPENDICES
1 Specifications for Aerosol Use.
2 Specifications for Foam Use.
3. Hydrocarbon Blend Refrigerants.
4. Specifications for Refrigeration Use.
5 UK Regulations on Storage and Transport of Flammable Gas Cylinders.
6. Fisk and Safety Phrases for Flammable Compressed Gases and Volatile Flammable Liquids -Mandatory in Product Labelling under EU Regulations.
7. Examples of Health, Safety and Environmental Publications by Government Agencies and IndustryAssociations in UK and USA.
8. Training Notes from UK Supplier Course on Safe Handling and Use of Hydrocarbons forRefrigeration Engineers.
9. Extracts from British Standard BS 4434; 1989"Safety Aspects in the Design, Construction and Installation of Refrigerating Appliances andSystems". Note: In process of being replaced by European Standard EN 378 - 1.
10. International Classifications for Transportation of Flammable Compressed Gases.
11. Purification of LPGs to Aerosol Propellant Grade - Extract from Aerosol Conversion TechnologyManual.
12. Costing Data on Possible Hydrocarbon Purification Scenarios.
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APPENDIX II
OORG OORG PublicationsReportNo.:
1. First OORG Refrigeration Working Group, "Reducing ODS Use by Developing Countries inRefrigeration", World Bank, Washington, D.C., October 1992.
2. First OORG Foams Working Group, "Reducing ODS Use in Foam-Blown Pre-InsulatedPipes (with particular reference to Poland)", World Bank, Washington, D.C., December1992.
3. First OORG Refrigeration/Freezer Insulating Foams Working Group, "Reducing OzoneDepleting Substance Use in Developing Countries in Domestic Refrigerator/FreezerInsulating Foams", World Bank, Washington, D.C., October 1993.
4. First OORG Production Working Group, "Technical Considerations for ChlorofluorocarbonAlternatives Production in Developing Countries", World Bank, Washington, D.C., October1993.
5. Fourth OORG Meeting, "The Status of Hydrocarbon and Other Flammable Altematives Usein Domestic Refrigeration", World Bank, Washington, D.C., October, 1993.
6. OORG Production Sector, "CFC-12 to HCFC-22 Plant Conversion: OORG ProductionSector Case Study", World Bank, Washington, D.C., February 1994.
7. Second OORG Refrigeration Working Group, "Domestic Refrigeration RefrigerantAlternatives", World Bank, Washington, D.C., May 1994.
8. Second OORG Foam Pre-Insulated Pipe Working Group, "Zero ODS Foam Pre-InsulatedPipe Alternatives", World Bank, Washington, D.C., May 1994.
9. Second OORG Refrigerator/Freezer Foan Working Group, "Transitional and Zero ODSDomestic Refrigerator/Freezer Insulating Foam Alternatives", World Bank, Washington,D.C., May 1994.
10. First OORG Chiller Working Group, "Chiller Refrigeration ODS Phase-out Alternatives"World Bank, Washington, D.C., July 1994.
11. First OORG Mobile Air Conditioning Systems (MACS) Working Group, "Mobile AirConditioning Systems (MA CS) Conversion to Zero-ODS Technology", World Bank,Washington, D.C., January 1995.
12. OORG Production Sector, "The Availability of Hydrocarbons for ODS Phaseout in DevelopingCountries", World Bank, Washington, D.C., April 1995.