AU676930B2

AU676930B2 - Fuel blends

Info

Publication number: AU676930B2
Application number: AU72231/94A
Authority: AU
Inventors: Robert William Killick; Lawrence Harold Parnaby; Peter Ronald Wrigley
Original assignee: Victorian Chemical International Pty Ltd
Current assignee: VICOL PETROLEUM Pty Ltd
Priority date: 1993-07-16
Filing date: 1994-07-15
Publication date: 1997-03-27
Anticipated expiration: 2014-07-15
Also published as: AU7223194A

Description

OPI DATE 13/02/95 APPLN. ID 72231/94 AOJP DATE 23/03/95 PCI NUMBER PCT/AU94/00401 AU9472231 (51) International Patent Classification 5: (11) International Publication Number: WO 95/02654 1/0 1 10,1/1 Al (43) Interna ional Publication Date 26 January 1995 (26.01 (21) International Application Number: PCT/AU94/00401 (81) Designated States: AM, AT, AU, BB, BG, BR, BY, CA, CHI, CN, CZ, DE, ES, Fl, GB, GE, HU), JP, KB, KG, KP, (22) International Filing Date: 15 July 1994 (15,07.94) KR, KZ, LIC, LT, LU, LV, MD, MG, MN, MW, NL, NO, NZ, PL, PT, RO, RU, SD, SE, SI, SIC TJ, TT, UA, US, 1)2, VN, European patent (AT, BE, CH, DE, DK, ES, FR, Priority Data: GB, GR, IE, IT, LU, MC, NL, PT, SE), QAPI patent (BF, PM0004 16 July 1993 (16.07.93) AU BJ, CF, CG, CI, CM, GA, ML, MR, NE, SN, TD), TG), ARIPO patent (KB, MW, SD).

(71) Applicant (for all designated States except US): VICTORIAN CHEMCAL INTERNATIONAL PTY LTD [AU/AU]; Published A.C.N. 006 083 012, 37-49 Appleton Street, Richmond, With international search report.

VIC 3121 (AU), (72) Inventors; and Inventors/Applicants (for US only): KII KM Robert, William 14 Dallas Street, Mount Waverley, VIC 3149 WRIGLEY, Peter, Ronald [AU/AU];,hu 28 Raleigh Street, Blackburn South, VIC 3130 o fTL 3 PARNABY, Lawrence, Harold [AU/AU]; 20 Baratta Street,U Blackburn South, VIC 3130 (AU).

(74) Agent: FREEHILL PATENT TRADE MARK SERVICES; Level 47, 101 Collins Street, Melbourne, VIC 3000 (AU).

(54) Title: FUEL BLENDS (57) Abstract A fuel blend composition including a hydrocarbon liquid as defined, up to 20 of the total comxposition of ethanol and/or n-propanoi and up to 15 by volume of the total composition of a fatty acid and/or organic ester, WO 95/02654 PCT/AU94/00401 1 FUEL BLENDS Field of the Invention This invention relates to fuel blend compositions including a hydrocarbon liquid, low-alkyl alcohol and fatty acid and/or organic ester. Additionally, the invention relates to a fuel additive composition including a low-alkyl alcohol and fatty acid and/or organic ester, Background to the Invention Diesel oil, due to its cost and availability, continues to be the backbone for industry around the world being the principal fuel for use in trucks, ships, trains, some cars and other automotive equipment and different stationary types of engines.

It is well recognised that the combustion of diesel fuel in engines can be hazardous to the environment. In particular, the partial combustion of diesel fuel to carbon, carbon monoxide, and nitrogen oxides creates noxious black exhaust gases which are pollutants.

This problem is particularly observable in trucks and other automotive vehicles where noxious black exhaust gases can be seen being released into the environment, Attempts have been made over the years to address the environmental concerns associated with exhaust fumes from engines by using alcohols such as methanc-l (methyl alcohol) or ethanol (ethyl alcohol) as fuels. Such attempts, for instance, have generally established that 15% of ethanol and 85% diesel oil provides an acceptable burning capacity without the necessity of modifying existing diesel engines.

The problem with using ethanol or methanol as a fuel in conjunction with diesel oil is that ethanol or methanol are immiscible with diesel oil, that is, they cannot be uniformly mixed or blended into one phase without rapid separation into their component parts. Since they cannot be uniformly mixed into one phase and stored for easy use, the components must be mixed just prior to use by, for example, having independent fuel tanks with the components independently pumped and mixed just before the combined fuel is injected into the fuel chamber, Such a system is currently being used in the bus fleet of the Des Moines Transit Authority, Iowa, USA.

One attempt to address the problem of immiscibility was to form an emulsion of the diesel oil and ethanol using an emulsifier, An example of this is in Australian Patent No, 544,728 which discloses a composition having 84.5% diesel oil, 15% hydrated ethanol and emulsifier. The emulsifier is of the styrene butadiene co-polymer type in admixture with a high molecular weight polyethylene glycol dissolved in xylene, This mixture can show both batch to batch variation and instability as the diesel and ethanol separate in the fuel tank.

WO 95/02654 PCT/AU94/00401 2 An attempt has also been made to address the problem of immiscibility by forming a blend comprising a petroleum fuel, methanol and a higher alcohol having 10-16 carbon atoms as a solvent for the petroleum fuel and methanol. An example of this is disclosed in US Patent No. 4,527,995.

A further attempt to address the problem of immiscibility is disclosed in UK Patent Application No. GB 2,090,611 where combustible compositions are claimed containing gas oils, methanol and a fatty acid ester for use in diesel engines. The claimed combustible compositions comprises from 20% to 90% by volume of at least one gas oil, from 5% to by volume of methanol and from 5% to 60% by volume of at least one (C 1

C

3 alkyl ester of a (C 6

C

2 2 saturated or unsaturated fatty acid. The specificafion states that alcohols heavier than methanol such as butanol must be added in substantial portions and do not improve the cetane number.

The article entitled "Diesel Oil Substitution by Processed Plant Oils Engine and Vehicle Results" published in 1982 by two authors from Volkswagen do Brasil S.A. Brazil, compares tests conducted using a straight methyl ester of soya bean oil (MESO) as a fuel with a 75-25 gasoil-MESO blend and a 68-23-9 gasoil-MESO-ethanol (anhydrous) blend.

The article provides that plant-oil mono-esters used as gasoil extenders serve as co-solvents between gasoil and ethanol, thus permitting ready use of otherwise-incompatible ethanol.

However, the article provides that an increase in proportion of ester in the gasoil from a 25% ester content onwards results in the ethanol being substantially compatible in the gasoil.

In subsequent investigations leading to the present invention, it has surprisingly been found that fatty acids and/or organic esters having up to 15% by volume in the fuel blend composition function as a coupling agent between the hydrocarbon liquid and ethanol and/or n-propanol to form a single phase composition which is not prone to separation.

Summary of the Invention According to a first embodiment of the invention, there is provided a fuel blend composition mtig:a ydrocarbon liquid (as hereinafter defined), up to 20% by volume of the total composition of ethanol and/or n-propanol and up to 15% by volume of the total composition of a fatty acid and/or organic ester.

In a preferred embodiment of the invention, the fatty acid and/or organic ester component is between 1.5% and 11% by volume.

In another preferred embodiment of the invention, the fatty acid and/or organic ester 4/component is between 2% and 5% by volume.

WO 95102654 PCT/AU94/00401 3 The fatty acid component is der ved preferably from natural oils and fats such as lard, tallow and vegetable oils, for example, canola, palm, corn, sunflower and soya bean oils or from specific blends commercially produced by fatty acid manufacturers or from fatty acids made by synthetic means or mixtures thereof. The fatty acid is preferably "oleic acid". For those skilled in the art, this is understood to mean the commercially available liquid fatty acids in which the mono-unsaturated fatty acid is significantly present.

The organic ester component is selected preferably from fatty esters such as ethyl oleate, ethyl tallowate, iso-propyl oleate, butyl oleate, methyl oleate or methyl cocoate and/or other aromatic esters such as butyl benzoate and/or other aliphatic esters such as ethyl acetate or mixtures thereof and/or dicarboxylic acid esters such as dioctyl maleate.

In another preferred embodiment of the invention, the fuel blend composition also includes methanol, butanol, iso-butanol, tert-butanol or mixtures thereof.

In a preferred embodiment of the invention, the hydrocarbon liquid (as hereinafter defined) component is at least 40% by volume of the total composition and more preferably between 75% and 88%.

The term hydrocarbon liquid, as used in the specification, means diesel oil and gas oil and mixtures thereof.

According to a preferred embodiment of the invention, there is provided a process for producing a single phase fuel blend composition including the steps of: adding the ethanol and/or n-propanol to the hydrocarbon liquid to form a mixture at the alcohol phase and an oil phase and thereafter; adding the mixture of step to the fatty acid and/or organic ester; and mixing the resultant mixture until a single phase has been formed.

According to a further embodiment of the invention, there is provided a fuel additive composition including ethanol and/or n-propanol and a fatty acid and/or organic ester in respective amounts ranging from a ratio of 25:1 to 1:1. Up to 35% of the fuel additive composition is added to the hydrocarbon liquid to form a single phase cormpostion.

In a further preferred embodiment of the invention, a process to produce a single phase fuel blend composition is provided by: adding the ethanol and/or n-propanol and the fatty acid and/or portion of organic ester to form the additive composition and thereafter; adding the mixture of to the hydrocarbon liquid and mixing the resultant mixture until a single phase has been formed.

I

WO 95/02654 PCT/AU94/00401 4 Examples The carboxylate esters used in the examples are those manufactured at the premises of the Victorian Chemical Co., Richmond, Victoria, Australia and are sold under the "Esterol" brand name. The ethyl acetate was purchased from BP Chemicals Australia. The diesel oil is that purchased from pumps of major Australian oil companies such as Caltex Petroleum Pty Ltd. The ethanol (ethyl alcohol) is commercial material obtained frnm the CSR Distilleries, Yarraville Victoria, Australia and is known as Ethanol 100SG/F3 which contains 3% methanol.

The following is a non-limiting example of a process to produce Composition 1 below according to the invention.

Diesel oil (85ml) is placed in a 100ml bottle at ambient temperature and pressure. Ethanol (10.0 ml) is added to the bottle creating an oil phase and an alcohol phase. Methyl oleate is then added, a stopper applied to the top of the bottle and the resultant mixture is shaken for a period of approximately 30 seconds or such less or further period of time to allow proper mixing of the liquids to take place and a single phase to form, The mixture was allowed to stand to allow the contents to settle. A single phase is observed, Substantially the same method is used to produce the other compositions detailed below.

Product blends were made (as percentage v/v) as follows.

Composition 1 Diesel Oil 85.0 Ethanol 10.0 Methyl Oleate 100.0 Composition 2 Diesel Oil 80.0 n-Propanol 13.5 Methanol Ethyl Oleate WO 95102654 WO 9502654PCT/AU94/00401 Composition 3 Diesel Oil 80.0 Ethanol 15,0 Ethyl Acetate 100.0 Composition 4 Diesel Oil 80.0 Ethanol 15.0 Ethyl Tallowate 100.0 Composition Diesel Oil 82.0 Ethanol 15.0 Butyl Benzoate 100.0 Composition 6 Diesel Oil 82.0 Ethanol 15.0 Oleic Acid 100,0 Composition 7 Diesel Oil 83.0 Ethanol 13.5 Iso-Propanol Ethyl Oleate 100.0 WO 95/02654 WO 9502654PCT/AU94/00401 6 Composition 8 Diesel Oil 81.0 Ethanol 15.0 Ethyl Tallowate Ethyl Acetate 100.0 Composition 9 Diesel Oil Ethanol 14 Methanol I Ethyl Oleate 4 Butyl Benzoate I_ 100 Composition Gas Oil 74.5 Ethanol 20.0 Oleic Acid Iso-Propyl Oleate Composition 11 Diesel Oil 87.75 Ethanol Ethyl Oleate -2 100.0 Composition 12 Diesel Oil 94 Ethanol Ethyl Oleate -I 100Q WO 95/02654 WO 9502654PCT/AU94/00401 7 Composition 13 Diesel Oil 94.5 Ethanol Ethyl Oleate 100.0 Composition 14 Diesel Oil 94.8 Ethanol Ethyl Oleate 0.2 100.0 Composition Diesel Oil Ethanol Ethyl Oleate Composition 16 Diesel Oil 79 Ethanol Ethyl Oleate 6 Iso-Propanol flQ Composition 17 Diesel Oil 74 Ethanol Ethyl Oleate I..JI.

100 WO 95/02654 WO 9502654PCT/AU94/00401 8 Composition 18 Diesel Oil 94.8 Ethanol Oleic Acid 0,2 100.0 Composition 19 Diesel Oil 94 Ethanol Oleic Acid I_ 100 Composition Diesel Oil 88.5 Ethanol 10.0 Oleic Acid 100.0 Composition 21 Diesel Oil 82 Ethanol Oleic Acid

JA-Q

Compositioni 22 Diesel Oil 81.5 Ethanol 15.0 Ethyl Oleate WO 95/02654 WO 95/2654 PCT/AU94/00401 9 Composition 23 Diesel Oil 76 Ethanol Oleic Acid 4 100 Composition 24 Diesel Oil 74.5 Ethanol 20.0 Oleic Acid Isopropyl Oleate 215 100.00 -Composition Diesel Oil Ethanol Methyl Cocoate 100 !Composition 26i Diesel Oil 77 Ethanol Methyl Cocoate -3.

too Composition 27 Diesel Oil Ethanol Methyl Cocoate

I

WO 95/02654 WO 9502654PCT/AU94/00401 Comp osition 28 Diesel Oil 78.5 Ethanol Ethyl Oleate n-Propanol 14.5 i1Q21Q Composition 29 Diesel Oil Ethanol Methyl Oleate 100 Composition Is Diesel Oil 77.5 Ethanol 1510 Ethyl Oleate Ethyl Acetate 2j Co mposition.31 Diesel Oil 77 Ethanol Dioctyl mnaleate 100 Composition 32 Diesel Oil Ethanol Ethyl Oleate 100 WO 95/02654 PCT/AU94/00401 11 Composition 33 Diesel Oil 67 Ethanol 18 Ethyl Oleate 100 All of the above Compositions had a single phase demonstrating the effectiveness of the use of levels of fatty acids and/or organic esters or mixtures thereof to blend hydrocarbon liquids such as diesel oil and low-alkyl alcohols such as ethanol into one phase. These compositions were tested over the typical temperatures in which normal fuels are to perform and were not found to be temperature sensitive, In each of the Compositions listed above, the blend of diesel oil and low alkyl alcohol is in one phase and the blend was found to operate satisfactorily as a fuel.

Volkswagon Engine: A 1979 Volkswagon "Golf" 4 cylinder 1.5 litre diesel engine was tested over the several months on Composition No 15, The engine was tested under normal operating conditions and no decrease in either power or fuel efficiency was noticed, Prime Mover Engine: A modem Mercedes Benz Prime Mover Engine Type 2228V Series was tested on Composition No 4, under typical 40 tonne loads. There was no noticeable decrease in either power or fuel efficiency of the engine, Fork Lift Engine: A 4 cylinder Yale Forklift (Model GDP 050 RUAS) (with a) 44HP (2400 rpm) Mazda XA series diesel motor engine was tested under typical warehouse operating conditions on Composition Nos 15 and 21 over several months. As well as no difference being noted in the efficiency of the forklift engine, the use of the ethanol blend is likely tto be more acceptable in the enclosed warehouse atmosphere.

In respect of each of the above compositions, a fuel additive composition can be formed of the low-alkyl alcohol and the fatty acid and/or organic ester which may be adde' to the hydrocarbon liquids, Fuel Additive Compositions The Additive Composition is illustrated by the following non-limiting examples. The following is a non-limiting example of a process to produce Additive Composition I below according to the invention.

Ethanol (66.7 ml) is placed in a 100 ml bottle at ambient temperature a 'I pressure, Methyl Oleate (33.3 ml) is added to the bottle to form a clear Additive Composition 1. Additive Composition 1 (15 ml) is then added to diesel oil (85 ml), a stoppr applied to the top of the bottle and the resultant mixture is shaken for a period of approximately 30 seconds or 3 95/02654 PCT/AU94/00401 12 less or for the period of time to allow proper mixing of the liquids to take place and a single phase to form.

Substantially the same method is used to produce other Additive Compositions as detailed below.

Additive Compositions were made (as percentages v-v) as follows: Additive Composition 1 Ethanol 66.7 Methyl Oleate 3 100.0 Additive Composition 1 (15 mi) was added to diesel oil (85 ml).

Additive Composition 2 Ethanol Ethyl Tallowate I0oQ Additive Composition 2 (20 mi) was added to diesel oil (80 ml).

Additive Composition Ethanol 79.4 Ethyl Oleate 11.8 Iso Propanol B8 Additive Composition 3 (17 ml) was added to diesel oil (83 ml).

,I 0 WO 95/02654 PCT/AU94/00401 13 Additive Composition 4 Ethanol 78.9 Ethyl Acetate 13.2 Ethyl Tallowate 7.9 100.0 Additive Corrposition 4 (19 ml) was added to diesel oil (81 ml).

Additive Composition Ethanol Ethyl Oleate n Butanol 100 Additive Composition 5 (20 ml) was added to diesel oil (80 ml), Additive Composition 6 Ethanol 83.3 Oleic Acid 16.7 100.0 Additive Composition 6 (24 ml) was added to diesel oil (76 ml).

Additive Composition 7 Ethanol 78.4 Oleic Acid 11.8 Iso Propyl Oleate 98 Additive Composition 7 (25.5 ml) was added to diesel oil (74.5 ml).

WO 95/02654 PCT/AU94/00401 14 Additive Composition 8 Ethanol Methyl Cocoate 100 Additive Composition 8 (30 ml) was added to diesel oil (70 ml).

Additive Composition 9 Ethanol 66.7 Ethyl Acetate 11.1 Ethyl Oleate 22.2 100.0 Additive Composition 9 (22.5 ml) was added to diesel oil (77.5 ml).

Additive Composition Ethanol 57.2 Ethyl Oleate 42.8 100.0 Additive Comoosition 10 (25 ml) was added to diesel oil (65 ml).

The resultant mixtures were allowed to stand to allow the contents to settle, All of the resultant mixtures had a single phase throughout the typical temperature range in which normal fuels are to perform and were found not to be temperature sensitive.

Claims

1. A fuel blend composition in-hidinu a hydrocarbon liquid as hereinbefore defined, up to 20% of the total composition of ethanol and/or n-propanol and up to 15% by volume of the total composition of a fatty acid and/or organic ester.

2. A fuel blend composition according to claim 1 wherein the fatty acid and/or organic ester component is between 1.5% 11% by volume of the total composition.

3. A fuel blend composition according to claim 1 wherein the fatty acid and/or organic ester component is between 2% 5% by volume of the total composition.

4. A fuel blend composition according to any of claims 1 to 3 wherein the fatty acid is derived from natural oils and fats or vegetable oils or is produced by synthetic means or any mixtures thereof.

A fuel blend composition according to claim 4 wherein the natural oils and fats are lard and tallow.

6. A fuel blend composition according to claim 4 wherein the vegetable oils are derived from canola, palm, corn, sunflower oil or soya bean oils.

7. A fuel blend composition according to any of the claims 1 to 3 wherein the organic ester is selected from fatty acids, aromatic esters and/or aliphatic esters and any mixtures thereof.

8. A fuel blend composition according to claim 7, additionally including a dicarboxylic acid ester.

9. A fuel blend composition according to claim 7 wherein the fatty acids are selected from ethyl oleate, methyl oleate, ethyl tallowate, iso-propyl oleate, butyl oieate, methyl oleate or methyl cocoate.

A fuel blend composition according to claim 7 wherein the aromatic esters are selected from butyl benzoate and ethyl acetate.

11. A fuel blend composition according to claim 7 wherein the dicarboxylic acid ester is dioctyl maleate.

12. A fuel blend composition according to any of the previous clainis further including methanol, iso-propanol, butanol, iso-butanol, tertiary butanol and mixtures thereof.

13. A fuel blend composition according to any of the previous claims wherein the hydrocarbon liquid is at least 40% by volume of the total composition.

14. A fuel blend composition according to any of the previous claims wherein the hydrocarbon liquid is between 75% 85% by volume of the totW- composition.

I WO 95/02654 PCT/AU94/00401 16 A process for producing a single phase fuel blend composition according to any one of claims 1 to 14 including the steps of: a) adding the ethanol and/or n-propanol alcohol to the hydrocarbon liquid to form an alcohol phase and an oil phase; thereafter adding the mixture of step to the fatty acid and/or organic ester; and mixing the resultant mixture until a single phase is formed,

16. A process for producing a single phase fuel blend according to any one of claims 1 to 14 including the steps of: adding the ethanol and/or n-propanol to the fatty acid and/or organic ester; thereafter adding the mixture of step(a) to the hydrocarbon liquid and mixing the resultant mixture until a single phase is formed;

17. A fuel blend composition as hereinbefore described by reference to any of the examples.

18. A fuel additive composition inj1nding ethanol and/or n-propanol and a fatty acid and/or organic ester in respective amounts ranging from a ratio of 25:1 to 1:1.

19. A fuel blend compositiona-inl n the hydrocarbon liquid and up to 35% of the fuel additive composition as in claim 18. A fuel additive composition as hereinbefore described by reference to any of the examples. Intaronional aplleliton No. P'CT/AU 94/00401 INTERNATIONAL SEARCH REPORT A. CLASSIFICATION OF SUBJECT MATTER Int. C. 5 C10L 1/02, 1/10, 1/18 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) IPC C10L 1/02, 1/18 Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched AU IPC as above Electronic data base consulted during the international search (name of data base, and where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to Claim No. X US,A, 4248182 (MALEC) 3 February 1981 (03,02.81) 9-12) GB,A, 2090612 (INSTITUT FRANCAIS DU PETROLE) 14 July 1982 (14.07,82) X See claim 4 12,13) A US,A, 4920691 (FAINMAN) 1 May 1990 (01,05 A US,A, 5203878 (WOOMER et al)

20 April 1993 (20.04.93) Further documents are listed FX See patent family annex. in the continuation of Box C, Special categories of cited documents later document published after the international fiing date or priority date and not in conflict document defming the general state of the art which is with the application but cited to understapd the not considered to e o particular relevance principle or theory underlying the invention earlier document but published on or after the document of particular relevance; the claimed international filing date invention cannot be considered novel or cannot be document which may throw doubts on priority claim(s) considered to involve an inventive step when the or which is cited to establish the publication date of document is taken alone another citation or other special reason (as specified) document of particular relevance: the claimed document referring to an oral disclosure, use, invention cannot be considered to involve an exhibition or other means inventive step when the document is combined document published prior to the international filing date with one or more other such documents, such but later than the priority date claimed combination being obvious to a person skilled in the art document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report 26 September 1994 (26.09.94) (3 Oc- 1994 C 10 .9 4- Name and mailing address of the ISA/AU Authorized officer AUSTRALIAN INDUSTRIAL PROPERTY ORGANISATION PO BOX 200 WODEN ACT 2606 AUSTRALIA G. Carter Facsimile No. 06 2853929 Telephone No. (06) 2832154 Form PCT/ISA/210 (continuation of first sheet (July 1992) copgid P'C1/AU 94/00401 INTERNATIONAL SEARCH REPORT C(Continuation). DOCUMENTS CONSIDERED TO BE RE LEVANT Category Citation of document, with indication, where appropriate of the relevant passages Relevant to Claim No. A US,A, 3672854 (ROSENWALD et al) 27 June 1972 (27.06,72) A US,A, 3667152 (ECK -RT) 6 June 1972 (06.06.72) Y,A GBA, 2090611 (INSTITUT FRANCAIS DU PETROLE) 14 July 1982 (14.07.82) (1-13) A WO;A, 93 24593 (GREENBRANCH ENTERPRISES, INC, 9 December 1993 (09,12.93) A AU,B3, 24 129/45 (131778) (VACUUM OIL COMPANY PTY. LTD.) 31 March 1949 (31.03.49) A AUA, 77656/8 1 (MASSEY-FERGUSON PERKINS LIMITED) 27 May 1982 (27.05,82) YA GBA, 2090613 ((INSTITUT FRANCAIS DU PETROLE) 14 July 1982 (1-13) (14.07.82) J I Form PCTIISA/21O (continuation of second shect)QJuly 1992) copgid 111 A A rl lAA I IVIIAl, biALALi tLI U'OIU'I lr101iltl0111lI liappllll0ll No, nitornla'lon kilt ipont Ully IIicIiU) PC'rT/AU 94/00401 This Annex lists the known publication level patent family members relating to the patent documents cited in the above-mentioned international search report. The Australian Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent Document Cited in Search Patent Flamily Member Report US 4248182 GB 2090612 DE 3150989 FR 2497223 BR 8108111 BR 8108559 DE 3149170 DE 3150988 FR 2498622 GB 2090611 GB 2090613 FR 24961 9 FR 2497222 US 4920691 US 5203878 AU 40342/93 IL 105415 WO 9322406 US 3672854 US 3667152 BE 750440 AT 301730 DE 207 ES 379969 GB 1264058 NL ?"Z FR 2047632 ZA 7002969 GB 2090611 BR 8108111 DE 3149170 FR 2496119 BR 8108488 BR 8108559 DE 3150988 DE 3150989 FR 2498622 GB 2090612 GB 2090613 FR 2497223 FR 2497222 WO 9324593 AU 43971/93 AU 77656/81 NZ 198995 GB 2090613 BR 8108559 DE 3150988 FR 2497222 BR 8108111 BR 8108488 DE 3149170 DE 3150989 FR 2498622 GB 2090611 GB 2090612 FR 2496119 FR 2497223 END OF ANNEX Form PCT/ISA/210(patent family annex)(July 1992) copgid