AU697333B2 - A fuel blend based on diesel and/or gas oil and C3-C22 alcohols - Google Patents

Description

WO 95/03376 PCT/AU94/00420 A FUEL BLEND BASED ON DIESEL AND/OR GAS OIL AND C3-C22 ALCOHOLS Field of the Invention This invention relates to fuel blend comprising a hydrocarbon liquid and one or more higher molecular weight organic alcohols.

Background to the Invention Diesel oil, due to its cost and availability, continues to be the backbone for industry around the world I 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 iC environment. In particular, the partial combustion oi 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 methanol (methyl alcohol) or ethanol (ethyl alcohol) as fuels. Such attempts, for instance, have established that 15% of ethanol and 85% diesJl 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 :i -17- :t 1 r:- WO 95/03376 PCT/AU94/00420 2 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 instabil 'y as the diesel and ethanol separate in the fuel tank.

Ai. 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 comprise 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

22 saturated or unsaturated fatty acid. The specification states that in relation to agents that render methanol and gas oils compatible, reference may be made to alcohols heavier than methanol such as butanol, but such substances must be added in substantial portions and do not have any favourable effect on the cetane number of the fuel.

In subsequent investigations leading to the present invention, it has been found that a composition including a hydrocarbon liquid and a higher molecular weight C 3 (excluding n-propanol) C 22 organic alcohol forms a single phase composition which is not prone to separation.

1/ S WO 95/03376 PCT/AU94/00420 3 Summary of the Invention In a first embodiment of the invention, there is provided a miscible fuel blend consisting of diesel fuel oil and one or more alcohols selected from C 3 (excluding n-propanol)-C22 organic alcohols and with no added water.

In this specification, the term higher molecular weight organic alcohol means any alcohol from 3 carbon atoms (excluding n-propanol) to 22 carbon atoms. Additionally, the term hydrocarbon liquid, as used in this specification, means diesel oil and gas oil and mixtures thereof.

In a preferred embodiment of the invention, the alcohol content of the fuel blend composition is up to 60% by volume of the total composition and preferably is between 10% and The higher molecular weight organic alcohol is preferably selected from iso-propanol, butanol, isobutanol, tert-butanol, 2 ethyl hexanol, iso-octanol, decanol and oleyl alcohol or mixtures thereof.

In another preferred embodiment, the fuel blend composition may additionally include an immiscible alcohol such as ethanol and/or n-propanol or a mixture having two or more of ethanol, n-propanol Sand methanol. The term immiscible alcohol, as used in this specification, means ethanol and/or n- S propanol or a mixture having two or more of ethanol, n-propanol and methanol.

In another preferred embodiment of the invention, the immiscible alcohol is up to 20% by volume of the total composition and preferably between 10% and 15%, and the higher molecular weight organic alcohol is up to 20% by volume of the total composition and preferably up to 10% of the c total composition.

SIn a preferred embodiment of the invention, the hydrocarbon liquid is at least 40% by volume of the ,Ei. total composition. In a further preferred embodiment, the hydrocarbon V I i

I

:A 4 WO 95/03376 PCT/AU94/00420 4 liquid is preferably up to 80% by volume of the total composition. In yet a further preferred embodiment, the hydrocarbon is up to 95% by volume of the total composition.

It has surprisingly been found that the higher molecular weight organic alcohol forms a single phase composition with the hydrocarbon liquid and the composition is not prone to separation. It has also been surprisingly found that the higher molecular weight organic ,cohol will couple the immiscible alcohol with the hydrocarbon liquid to formnn a single phase.

According to a preferred embodiment of the invention, there is provided a process for producing a fuel blend composition including the steps of: adding the higher molecular weight organic alcohol to the hydrocarbon liquid and thereafter; blending the resultant mixture until a single phase has been formed.

In a further preferred embodiment of the invention, step involves adding in any order the higher molecular weight organic alcohol and the immiscible alcohol to the hydrocarbon liquid.

According to a preferred embodiment of the invention, there is provided a fuel additive composition including the immiscible alcohol and the higher molecular weight alcohol in respective amounts ranging in a ratio of 0-25:1. Up to 60% by volume of the fuel additive composition is added to the hydrocarbon liquid to form a single phase composition.

In a further preferred eml'od,'ment of the invention, a process to produce a single phase fuel blend composition is provided by: adding the higher molecular weight organic alcohol and the immiscible alcohol 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.

O- si:; WO 95/03376 PCT/AU94/00420 Examples The diesel oil used in the examples is that purchased from pumps of major Australian oil companies such as Caltex Petroleum Pty Ltd. The ethanol (ethyl alcohol) and iso-propanol are commercially available materials obtained from the CSR Distilleries,- Yarraville, Victoria, Australia where the ethanol is known as Ethanol 100SG/F3 which contains 3% methanol. The oleyl alcohol was purchased from Henkel Australia and all other compounds used in the examples were purchased from ICI Australia Limited.

The invention is illustrated by the following non-limiting examples of Compositions.

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

Diesel oil (80ml) is placed in a 100ml bottle at ambient temperature and pressure. Ethanol and n-butanol (5ml) are added to the bottle, a stopper applied to the top of the bottle and the resultant mixture is shaken for a period of approximate"y 30 secodJs 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, is then allowed to stand to allow the contents to settle. A single phase is observed.

Substantially the same meth,:- is used to produce the other compositions detailed below.

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

Composition 1 Diesel Oil 80.0 Ethanol 15.0 n-Butanol 100.0 Composition 2 Diesel Oil 50.0 SIso-Butanol 50.0 100.0 I; 7T .7 WO 95/03376 PCT/AU94/00420 6 Composition3 Diesel Oil 85.0 Iso-Propanol 15.0 100.0 Composition 4 Gas Oil 85.0 Ethanol Iso-Propanol 100.0 Composition Diesel Oil 80.0 Methanol Ethanol 13.5 Iso-Butanol 100.0 Comiposition 6 Diesel Oil 80.0 Ethanol 15.0 Iso-Octanol 100.0 Composition 7 Diesel Oil 75.0 Ethanol 20.0 Oleyl 100.0 Composition 8 Diesel Oil 40.0 Gas Oil 40.0 n-Butanol 20.0 WO95/03376 PCT/AU94/00420 Composition 9 Diesel Oil 77.0 JEthanol 20.0 Oleyl Alcohol 100.0 Composition Diesel Oil 77.0 Ethanol 20.0 2 Ethyl Hexanol 100.0 Composition.11 Diesel Oil 94.0 Ethanol n-Butanol 100.0 Composition-12 Diesel Oil 76.0 Ethanol 20.0 Ethyl Hexanol 100.0 Composition 13 Diesel Oil 94.0 Ethanol Iso-Propnol 0- CompositionLr 14 Diesel Oil 94.0 Ethanol 2 Ethyl Hexanol 100.0 WO 95/03376 PCT/AU94/00420 8 Composition Diesel Oil 94.8 Ethanol Decanol 0.2 100.0 Composition 16 Diesel Oil 77.0 Ethanol 20.0 Decanol 100.0 Composition 17 Diesel Oil 94.0 Ethanol Oleyl Alcohol 100.0 Compsitin 1 n-Butanol 10.0 100.0 Composition 19 Diesel Oil 65.0 Ethanol 20.0 4n-Butano1 15.0 00 Composition Diesel Oil 75.0 Ethanol 20.0 100.0 Composition 21 Diesel Oil 90.0 Oleyl Alcohol 10.0 WO 95/03376 PCTIAU94/00420 9 Composition 22 Diesel Oil 90.0 Ethanol n-Butanol Iso-Octanol 100.0 Composition 23 Diesel Oil 80.0 Ethanol 10.0 n-Butanol 10.0 100.0 All of the above Compositions had a single phase demonstrating the effectiveness of the use of the higher molecular weight organic alcohol to blend with the hydrocarbon liquid or the use of a higher molecular weight organic alcohol and the immiscible alcohol to blend with the hydrocarbon liquid to form one phase. These Compositions were tested over the j typical temperatures in which normal fuels are to perform and were found not to be temperature sensitive.

In each of the Compositions listed above, the Composition was found to operate satisfaLtorily as a fuel.

Fork Lift Engine dA 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 No 23. As well as no difference being noted in the efficiency of the forklift engine, the use of the Composition was more likely to be more acceptable in the enclosed warehouse atmosphere.

In respect of each of the above Compositions 4, 5, 6, 7, 9-20, 22 and 23), a fuel additive composition can be formed of the higher molecular weight organic alcohol and the immiscible alcohol.

WO 95/03376 CT/AU94/00420 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 1 below according to the invention.

Ethanol (87.0 ml) is placed in a 100 ml bottle at ambient temperature and pressure. Oleyl alcohol (13.0 ml) is added to the bottle to form a clear Additive Composition 1. Additive Composition 1 (23 ml) is then added to diesel oil (77 ml), a stopper applied to the top of the bottle and the resultant mixture is shaken for a period of approximately 30 seconds or 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 87 Oleyl Alcohol 13 100 Additive Composition 1 (23 ml) was added to diesel oil (77 ml).

Additive Composition 2 Ethanol 87 2 Ethyl Hexanol 13 100 i Additive Composition 2 (23 ml) was added to diesel oil (77 ml).

WO 95/03376 PCT/AU94/00420 11 Additive Composition 3 Ethanol 83.3 n-Butanol 16.7 100.0 Additive Composition 3 (6 ml) was added to diesel oil (94 ml).

Additive Composition 4 Ethanol 96.2 Oleyl Alcohol 3.8 100.0 Additive Composition 4 (5.2 ml) was added to diesel oil (94.8 ml).

Additive Composition Ethanol n-Butanol 100 Additive Composition 5 (20 ml) was added to diesel oil (80 mi).

Additive Composition 6 Ethanol n-Butanol Iso-Octanol 100.0 V- Additive Composition 6 (10 ml) was added to diesel oil (90 mi).

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.

i 1

Claims (7)

1. A miscible fuel blend consisting of diesel fuel oil and one or more alcohols selected from C 3 (excluding n-pi opanol)-C 2 2 organic alcohols and with no added water.

2. A miscible fuel blend composition according to claim 1 wherein the alcohol content is up to by volume of the total composition.

3. A miscible fuel blend composition according to claims 1 or 2 wherein the alcohol content is between 10% and 20% by volume of the total composition.

4. A miscible filel blend composition according to any of the previous claims wherein the C 3 (excluding n-propanol)-C 22 organic alcohol is selected from iso-propanol, butanol, iso- butanol, tert-butanol, 2 ethyl hexanol, iso-octanol, decanol, oleyl alcohol or mixtures thereof.

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

6. A miscible fuel blend composition according to any one of claims 1 to 5 wherein the hydrocarbon liquid component is up to 80% by volume of the total compo.ition. S7. A miscible fuel blend composition according to any one of claims 1 to 5 wherein the hydrocarbon liquid component is up to 95% by volume of the total composition. i il It *ecuignp pno)C2ogncachl adwt oaddwtr Amsil ulbedcmoiinacrig ocam1weenteachlcneti pt L. IILUl- iu uI u L.umu1pu ILn .U 1 uiuiig t1 any one or claims I to 3 wherein the hydrocarbon liquid component is up to 80% by volume of the total composition.

7. A miscible fuel blend composition according to any one of claims 1 to 5 wherein the hydrocarbon liquid component is up to 95% by volume of the total composition. j4.' 'rl .a INTERNATIONAL SEARCH REPORT International application No. PCT/AU 94/00420 Ii ~I A. CLASSIFICATION OF SUBJECT MATTER Int. C. 5 C10L 1/02 Acording tc 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 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) (1-13,15-18) X US,A, 4753661 (NELSON et al) 28 June 1988 (28.06.88) (1-13,15-18) X US,A, 3817720 (MOY et al) 18 June 1974 (18.06.74) (1-3 X GB,A, 2090612 (INSTITUT FRANCAIS DU PETROLE) 14 July 1982 (1,3) (14.07.82) P,X WO,A, 9324593 (GREENBRANCH ENTERPRISES, INC.) 9 December 1993 (1) (09.12.93) S Further documents are listed X See patent family .nex. in the continuation of Box C. Special categories of cited documents later document published after the internationai filing date or priority date and not in conflict document defining the general state of the art which is with the application but cited to understand the not considered to be ofparticular 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 docume'.t which may throw doubts on priority claim(s) considered to involve an inventive step when the or which is cited to establish the rublication date of document is taken alone another citation or other special i eason (as specified) document of particular relevance; the claimed document referring to an oral dis losure, 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 internatior al search Date of mailing of the international search report 23 September 1994 (23.09.94) a Qc. V\ 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) copjne tl Al '1 m C A INTERNATIONAL SEARCH REPORT International application No. PCT/AU 94/00420 C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT Category* x x x x x x Citation of document, with indication, where appropriate of the relevant passages Relevant to Claim i1- DE,A, 2949118 (BASF AG) 11 June 1981 (11.06.8 1) DE,A, 2949535 (BASF AG) 11 June 1981 (11.06.8 1) EP,A, 319060 (ENIRCERCHE 7 June 1989 (07.06.89) AU,B, 178 16/83 (574045) (ETHYL CORP.) 23 February 1984 (23 .02.84) AU,A, 22217/83 (UNION CARBIDE CORPORATION) 14 June 1984 (14.06.84) GB,A, 2090613 (INSTITUT FRANCAIS DU PETROLE) 14 July 1982 (14.07.82) (1-13,15-18) (1-13,15-18) (1-13,15-18) (1,8-13, 17, 18) (1-13) Form PCTIISAt210 (continuation of second sheet)(July 1992) copjne k K 4, i INTERNATIONAL SEARCH REPORT International applica,:on No. PCT/AU 94/00420 Box I Observations where certain claims were found unsearchable (Continuation of Item 1 of first sheet) This international search report has not established in respect of certain claims under Article 17(2)(a) for the following reasons: 1. Claims Nos.: 14,19 boc.ra~o !iu; reiha to bjut: mgttor not rrlquirar tz bo larohohd by thit Authority, namly: because they rely on references to the examples, and thus do not comply with Rule 6.2(a). 2. Claim Nos.: because they relate to parts of the international application that do not comply with the prescribed requirements to such an extent that no meaningful international search can be carried out, specifically: 3. Claims Nos.: because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4(a). Box II Observations where unity of invention is lacking (Continuation of item 2 of first sheet) This International Searching Authority found multiple inventions in this international application, as follows: 1. As all required additional search fees were timely paid by the applicant, this international S search report covers all searchable claims 2. As all searchable claims could be searched wit' iut effort justifying an additional fee, this Authority did not invite payment of any additioal fee. 3. As only some of the required additional search fees were timely paid by the applicant, this S international search report covers only those claims for which fees were paid, specifically claims Nos.: 4. No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims; it is covered by claims Nos.: Remark on Protest D The additional search fees were accompanied by the applicant's protest. No protest accompanied the payment of additional search fees. Form PCT/ISA/210 (continuation of first sheet(l))(July 1992) copjne ii i :-s ii ii i i 1f k X: i;i INTERNATIONAL SEARCH REPORT Information orl patent family membe International application No. PCT/AU 94/00420 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 Family Member Report US 4248182 NIL US 4753661. NIL US 3817720 NIL GB 2090612 BR 8108488 DE 3150989 FR 2497223 BR 8108111 BR 8108559 DE 3149170 DE 3150988 FR 2498622 GB 2090611 GB 2090613 FR 2496119 FR 2497222 WO 9324593 AU 34971/93 DE 2949118 BR 8007971 DE 2949535 ZA 8007610 EP 319060 IT 1223404 AU 17816/83 BR 8304389 CA 1195117 EP 101093 EP 195462 EP 338599 JP 59084984 US 4420311 CA 1196499 US 4417903 CA 1228854 CA 1243206 US 4421522 US 4405334 US 4405335 US 4405333 CA 1195116 US 4406665 ZA 8305855 AU 22217/83 BR 8306743 CA 1224628 DK 5653/83 EP 117915 FI 834504 JP 59115390 NO 834525 NZ 206521 ZA 8309156 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 SEND OF ANNEX Form PCTIISA/210(patent family annex)(July 1992) copjne a c :A