CA2131450A1 - Fortified hydrocarbon and process for making and using the same - Google Patents

Abstract

A fortified hydrocarbon comprises a mixture of a major portion by weight of hydrocarbon base and as an additive a minor portion by weight of methyl ethyl ketone together with tertiary butyl alcohol and/or with methyl tertiary butyl ether. The formulation is useful as a torch gas for cutting metal, a fuel for internal combustion engines or as a heating gas.

Description

W~ RCr/T~Z93/0001 2 FORTIFIED HYDROCARE~ON AN~ PROCESS FOR
MAXING AND US ING THE SAME
"'` ;' The present invention relates to hydrocarbons including gas for use in cutting and/or welding torches, internal- .
combustion engine fuels and high temperature heating gas and oil fortified by the addition of a double additive :~
or conditioner.
various attemp~s have been mad~ pr~viously to impro~e gas used in cutting and~or welding torches ~y adding an aclditive or a double addi~ive to them. Th~se prior art gases h~ve been composed of various -~:
hydrocarbons from methane to octane and some have included propane and ~utane. Harri~ U~S. Pa~ent No. ~:
1,5~5,9~5, issued December 15, 1~25, for example, .: ~
forti~ied a wet casingh~ad gas cs:~mposed of me~hane, ethane~ propane, butane a:nd hexane by;~he addition of .
ethyl ether or methyl eth~er. Another patent that ;-propo~ed ~o add ethyl ~ith~r or ethyl oxid~ to a ga~ :~
including prvpane or butane and propane i~:U.S~ Patent Mo. 2,513,769, i~suad~Jul~y~4~ 50 (White)~
British Patent s~eci:Eication No. 813,981,~published -May 27, 1~59 (O ~ -Ferrolel~e LLmited) propoBed~ to add to ~ydr~car~on gas an oxygen-containing compound such as i~opropyl e~her, methyl i~30propyl e~her,~ methyl propyl ether, normal propyl et~er, ethanol and methanol.
British Patent~ NoO~8:L3,981 sugg~sts the : ~ :
incorporation of more than one compound but does no~
~uggest any specific doub]Le compounds. Seley U.S. ~i:

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WC~9~ 3 ~ ~s~ PCI/NZ93tO0012 Patent No. 2,411,759, issued November 26, 1946, does suggest the use of double additives, namely, ethyl oxide and benzine.
The Whi~e U.S. patent ~o. 2,951,750, i~ued Sep~ember 6, 1960, refer~ to the prior double additiv~s for torch gas of dLmethyl ether and benzine ~t column 1, -~' lines 21 ~o 25, presllmably as disclosed in the Seley patent, and then proposes the use of the double additive of propylene oxide and dLmethyl ether at column 1, lines 55 to 62 r instead of usinq benzine and dimethyl ether.
In addi tion, Kesslex U . S . Patent No . 3 ~ 591, 355, :~
issued July 6, 1971, proposed the addition of a double additive to torch ga~, composed of a liquid alkanol ~uch ~ ;
as methanol and a mixkure c: f alkane~ such as pentane and iSopentan~3~ Whiîe U.5. Pateht No. 3,989,479, issued November 2, 1976, also proposed the addition o~ methanol :~
and British Patent No. 56~,1û8, accepted May 4; 1945, ~ ~ :
pr~posed the addition o ammonia. This British pat~nt also recolTunended increasing the amount of propane in producer gas, water gas, MLond gas and other commercially ~vailable gas mixtures in which methane predc~minated.
Medsker U~S. Patent ~o. 2f908~599r issued October 13, 1959, stated that methyl :borate and acetone had been . ., .~.
used previou51y in a fuel for torch use citing Ui.S.
Patent No. 2,281~910. ~he M~dsker patent proposed a ;
mixture of methyl borate and hexane as an additive f or a ~aseous fuel. The Bialosky et al. Patent No. 2,281,910, :-issued May 5 , 1942 t discloses a liquid flux containing ~:
- - 2 ~

WC) 9~/ IXI 16 ~ ?, ~ PCT/~Z93/00012 methyl bora-te and a ketone, such as acetone or methyl : :.
ethyl ketone, to be subjected to a stream of ace~ylene, ~ ;:
hydrogen or similar combustible gas for coating the work with boxic acid or oxide. -~
The principal torch gas used previously has b~en acetylene which is comparatively expensive, difficult to store and to t~ansport, requires the u~e of almos~ pure oxygen with i~ and fo~ms persistently adherent scoria when used for cutting ferrous metal. -~.
Internal-combustion engine fuelsr ~uch as gasoline, have been inclined to detonate in reciprocating piston internal-cvmbustion engines, and it h s been found that high-oc~ane gasoline can reduce or elLminate detonation~
causing combustion knock and increase power. Another expedient used t~ de~er detonat:ion ha~ been the addition :
of antiknock material, particularly tetraethyl lead. ~-Also, aromatic amines ha~e been used in ~mounts averaging 2.6g. of metal per gallon. Such amin~s are .... -not commercially used, howeverJ because of their higher c~s~ than tetraethyl lead or mi~ed methyl ~th~l lead alkyls. Also, methylcyclopentadienyl manganese tricarbonyl has been used. In addition, u:se of other metallic antiknock compounds has been proposed~ such as ~.
thallium, seleniwm and tellurium organic compounds, but these have not proven ~o be useful. ~`~
A ~isadvantage of using tetra~thvl lead is that the `~
l~ad has been discharged into the air, and le~d is `~

_ 3 WO ~3/lX116 PCT/NZ93/00012 ~ 3~ ~
physically harmful, so that its use in gasoline for internal combustion engines has been phased out. Methyl tertiary butyl ether by itself has been used as an additive for unleaded gasoline as an octane boos~er and ~;
~o reduce harmful emission products.
A principal object of this invention i5 to proYide :
fortified hydrocarbon such as torch gas having ;~
characteristics superior to those of acetylene, especially for cutting f~rrous metal, and also for welding. Such object also includes pro~iding fortified hydrocarbon having characteristics superior to those of hydrocarbon fortifi~d only by the addition of methyl ~;
ethyl ketone.
A p~rticular object is to provide a torch gas which ;.
will have high flame temperature and intense heating ~:
cap~bil ity . ...
A further object is to provide torch gas that can ;`~
~e stor~d and:transported easily and econ ically.
Another object is to pro~ide a torch gas haviny a base gas which is readily available in almost the entIre world, can b~ provided more economically and is easy to fortlfy for enhancing its~att~ibutes.
It is also an o~3ect~to provide a torch gas enabling ferrous metal to be cut faster and clea`ner. ~ ~.0~.
Another object is to provide~a gas:that can be used by torch~s for cutting un~er water at considerable ~
depths.

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WO 4?~ i 16 PCr/NZ93/00012

2 1 3 ~
An additional object is to provide a gas that can be used for torch cutting more economically because it will combine ef fe~:tively with oxygen containing a higher proportion of adulterating gases which cannot otherwi5e ; ~
be used with acetylene. ~:
The foregoing objects can be accomplished by -utilizin~ liquifi~d petroleum gas (LPG~ fortified with me~hyl ethyl ketone (MEK), together with ~tertiary butyl `-alcohol (T~A) and/~r wi~h methyl ter~iary bu~yl ether ;~;
~ " ~
(~TBE).
A further objeck of this invention is to provide fortified hydrocar~on for purposes other than ~:
torch gas, such as high t~mperature heating gas or oil `~
for heating industrial furnaces such as for melting metals for pouring, and blast furnaces. .~
This further obiect can be acc~mplished by . ~:
u~ilizing LPGt n~tura~ gas or liquid hydrocarbon, such :
as diesel oil or ~uel~oil fortified wlth ME~ together with ~BA or with MTBE.
Still another object is to fortify li~uid hydrocarbon, especiall~y~g~s~oline, ~or use as an internal-combustion engine~fuel to deter detonation and promote unif~rmity o co~bustlon.
This still furthe~ o~ject can be accomplishiad by adding ~o the gasoline MEK together with TBA or wlth MTBE as an additive.

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'''',' ', W(> ')~/181 16 ~ P~VNZ97/00012 Liquefied petroleum gas (LPG) is ~he preferred base gas for the fortified torch gas of the present invention because o~ its high butane and propane content. ~oth the n-butane and isobutane isomers of butan~ are usually pr~sent in LPG, but a substantial amount of butane can have been removed from LPG because of the demand from industry for butane derivatives, such a~ for fuel, in which case the LPG is composed largely of propane. It i~, howe~er~ desirable that there be a reasonable ~;
propor~on of butane in the LPG, such as from 5% to 40%. :~
.Alternatively/ the bas~ gas could be propane or butane ~ . ~
alone or any mixture of th~e gases or propyl~ne. ~:
The additive or conditioner u~ed tn fortify the base gas contains methyl ethyl ketone ~MEK3, otherwis8 ;~
known as 2-bu~anonP; havîng the formula CH3COCH2CH3 .
together with tertiary butyl alcohol, also known as tert~butyl alcohol (TBA), havin~ the formu3a (CH3~3COH ~ -or methyl tertiary butyl ether~ othe ~ ise known as methyl tert~butyl e~her (MTBE ) ha~ing ~he formula ..
(CH3)3COCH3. ME~ is a liq~id with a boiling point of 70.6 degrees C. and a specific gravity of: ~.8Q5 an~ 20 degrees C. At ambient temperature TBA is a waxy solid ..
which melts at ~5.6 degrees C. and has a~specific gravity ~ 0.779 at 26 degrees~C. At a~bient tempera~ure MTBE is :cvlourles5 liquid havlng a boiling ~ ;-point of 55 degrees C. and a freezing point of -110 degrees C. and has a specific gravity of 0.74. ~ ;
LPG must be stored under pressure to keep it in a `
liquid state, but relatively hea~y pressurized storage - 6 ~
~: ' WO93/l8116 PCT/N~93/00012 ~ ~ 3 ~ C ~ -tanks and handling equipment for LPG is commercially practical and customary.
Without being fortified, LPG mixed with oxygen is ~ :
not ~e~y affective for torch cutting and welding, not .
nearly as eff~ctive as acetylene gas mixed wlth substantially pure oxygen, but by enriching the base LPG
.. .
with ME~ together with MTBE or TBA as an additive th~
flame temperature is considerably increased and the ~::
heating capability is greatly Lmproved.
The amount of additive used will depend on the ~xtent to which it is desired to improve the characteristics of the base hydrocarbonl bu~ the~amount -of additive would ba within the r~nge of 0.5% to 20% of ~he hydrocarbon base gas by weight. The ~mount of TBA ~.
or MTBE is usually up to about 20% by weight of the amount of ~EK. For use in fortifying torch gas such as ~ ~:
LPG, an amount of TBA and/or MTBE up to 3% of the LPG by weight could be mixed with up to 15~ of M~R by weigh~ ~f ~PG, such as 3% to 10% MEK enh~nced with 1% to 3~ r~A
and/or MT~E of the base gas by~wQ ight. Suficiently , ~ , ben~ficial results are usually obtained by the use of 2%
' .
~f TB~ or NTBE by weight of the hydrocarbon base gas .
mixed wi~h lOg~ of MEK by weight of the hydrocar~on base ga~
For in~ernal-combu~tion engine fuel, the ratio of a~?out 20% of TBA and/or M~BE to MEK ~y weigh~ is preferxed, ~o tha~ TBA or M~E3E in the amount o~ 1% of ;`
the hydrocarbon base by weight can be mixecl with MEK in _ 7 _ ., .

WO 93~1Xllfi 1~ 0 PCT/NZ93/OOOt2 the amount of 5% of the hydxocarbon base by weight. For most purposes TBA or MTBE in the amount of 0.5% of the internal-combustion fuel by weight mixed with MEK in the ~::
amount of 2.5% or 3% of the internal-combus~ion engine :~
fuel by weight provides sufficient Lmprovement in ~-performance of the internal-combustion engine fuel.
The procedure for combining the additive with the hydrocarbon base gas is sLmple. MEK is a liguid at normal temperatures. To combine the TBA with MEK, the -~
T~A may be melted by subj~cting its container to warm water such as at a ~emperature of 40 degrees C to 45 degrees C and the TBA liquid is then sLmply mixed with j:
the MEK liquid before the additive liquid is mixed with the hydrocarbon. MTBE liquid can be ~ixed with the MEK
liquid before the additive liquid i5 mixed with the ~
hydroc~rbon. The additi~e is a liquid at normal ~-:
temperatures and is supplied to the s~orage tank in .
which the hydrocarbon is to be s~ored or transported~
It is quite practical to supply the additive to standard 55 gallon drums. - :
The additi~e can be supplied in conjunction with a ~ ~
catalyst, preferahly activated carbon in the form of . .`.
powder, granules or pellets. The activated carbon is :`~
~morphous, preferably ha~ing been produced from coal or petroleum coke. Alternative catalysts that can be used are platinium, cupric oxîde and granular sil~er carried by a suitable carrierO ~ ;~
;~.,..`.
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WO~3/lX1l6 L~ 1 3 1 ~ PCl/NZ93/000l2 '~
The amount of catalyst used is not critical, but it should be placed in the bottom of a storage container to ~`~
facilitate mixing of the additi~e with the hydrocarbon base gas when i~ is supplied to the container und~r pressure. An amount of such catalys~ between 1% and 5%
of the weight of the addi~ive would b~ satisfactory.
The resulting mixture of base gas and additive or conditioner will be azeotropic so that ~he fortified . :~
torch gas will be homogeneou~ when it is released fr~m the ~torage container to the torch. :~
In ord~r to provide an effective cu~ting flame, it ::~
is necessary to supp~y to an acetylene ~orch ox~gen that is in ~ubstantially pure form, such as ~ lea5t 99%
oxygen by volume. Satisfacto ~ cut~ing tempera~ures can ;
be provided by mixing with the fortiied bas~ gas of the ;~
pres~n~ in~ention less pur~ oxygen such as oxygen ha~ing a purity of approxLmately 95%, the adulterant bein~
nitrogenj carbon dicxide and other gas~components of air. Even when oxygen of 90~ purity is used, the fl~me~
temp~rature of base LPG of ap~roxLmately 2760 degrees C~ - .
(5,000 degrees F.) can be raised to approxL~ately 3200 degrees C. (5,800 degrees F.) to 3320 degrees C.~ ~6,000 degrees F. ) by use o:E the base LPG fortified by MEK and MTBE according t~ the present invent~on. Such Lmpure oxygen can be produced economically by compressing alr ;-to about 4,000 psi, chilling it to minus 218 degrees C
(minus 360 degrees F.~ whi~h liquefies the air and then .
allowing the tempera~ure of the 1i~uefied air to ribe _g_ ~

~ PC~/NZ93/OOOt2 gradually while venting the container to release the nitrogen componen~ of the liquified air which vaporizes at minus 196 degrees C. ~minus 320 degrees F.~ leaving the oxygen in liquid foxm. :
In other processes for producing Lmpur~ oxygen, nitrogen of the air .is removed by zeolite resulting in oxygen of gO% to 95~ purity.
An advantage of using the fortified base gas of the . ;~:
presen~ in~ention over acetylene for cu~ting fexrous ~:
metal is that a clean precise kerf is obtained~ -;
Oxya etylene cutting produces a hard scoria persis~ently adherent ~o the work which increases the heating : ;:
. . .
r~quired and usually must subseguently ~e chipped off th~ work. Vtilization of the fortified torch gas of the `~
present invention produce~ a soft friable scoria which ~;:
is sloughed off the work and out of the kerf as the ;~
cutting progres0es to lea~e a narrower clean kerf wi~h virgin metal along opposite margins of ~he kerf.
A particular advantage which the fortified torch -~
~as of the present inventi~n has is that it can~be used: ;
: ~.
for flame cutting under water to a depth of 300 feet.
The use of the oxyacetylene torch is limited to 20 fee~
under water because at~pressures ~o whic~ it would be: : '~!`(`
necessary to subject the~gas to enable it to be dispensed to ~he cuttlng torch at greater depths~the -acetylene will explode. Conseguen~ly7 the only ~ :
alternati~e that has been availa~le for cutting under ;.
water at depths greater than about ~0 feet p~lor to this .;

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WO g3/18116 is .~ PCT/NZ93~00012 invention has been the use of a carbon arc, the action of which is slow and the use of which is dangerous.
While the use of MEK i5 useful in expediting ~he cutting of ~etal, the use of ~EK enhanced by the ~:
addition of TBA has increased the cutting speed of me~al ~Erom 5% to 10% in comparison to the use of MEK alone, and the use of M13K and MrBE in combination has increased ;;
~he cutting speed ~o 20% to 25~ faster than where MEK .
has been us~d alone as an additi~e and abou~ 15% fas~r ~:~
than the cutting ~pe~d where the MEK has b~en enhanced with TBA.
In addition to use of the present inv~ntion:in fortified torch gas, the in~ention can be used for high ~emp~rature hydrocarbon heating gas ~uch as LPG or natural gas, and high-tempera~ux~ hydrocarbon heating liquids ,uch as boiler fuel oil, stove oil or other oil, used in ~uch industrlal~proc~sses as smelting or other ~-metal melting such as required for foundry casting, or for steam genera~ing. For such purpo~es, the additi~e can be within the range o~ 2% to I0~ o~ the hydrocarbon by weight. If the amount of additive is greater~than 5~, a cataly~t such as powdered acti~ated carbon should : ;;~
be used t~ facilitate thorQugh~mixing of the additive with the hydrocarbon.
Vse of the bydrocarbon gas such as LPG for soldering~ brazing o* light metal cutting is rendered mor~ e~fecti~e if th~ additive i5 mixed with the gas.
For such u~e it is preferable to us~ less additive than ;~
}n the case of torch gas for cutting or welding thick WO1~3/lXll6~ PCT/NZ93/00~12 metal. For soldering, brazing or light cutting, an amount of additive within the rang~ of 2% to $% by weight is adequate, and such an amount can be mixed :~
sufficien~ly intimately with ~he hydrocarbon gas without the use of a catalyst. . -Anoth~r use of the dditive is for fortifying ~
internal-combustion engine fuel, such as automotive -~:
ga~oline, aviation gasoline or diesel oil. ~or such use the additive functions as an antiknock agent as w~ll as ~:
improving ~h~ uniformity of combus~ion and accelerating the rate of combustion, which consequently enhances the power~producing characteristics of the fuel. ~;-For internal-c~mbustion engine fuel use, the range of additive used would be 0.5% to 6~ of the hydrocarbon ;-by weight but preferably within the range of l~ to 4% by weight.
~ . . - . .
~ s an additi~e for hydroca~bon base fuel, the amount of T~A or~MTBE less than 20% by weight o~the amount of MEK is preferred/ but the ~otal amount of TBA ~``
or ~ BE should:not:exceed 3% of the hydrocarbon;~ase~by weight in order~to maint~ain~azeotroplc~Gharacteristlcs~ ~ of the forti~ied~hydro~arbon~ For internal~-combustion~
engine fuel, the ratio~o:f~20%~of~TB~ or MTBE~to~ER by:~
weight~is preferred/ so:that ~ ~ or MTBE in the amount of 1% of the hydrocarbon~base by welght:can be mixed with MEK in the~amount of 5% of;the hydrocar~on~base~by weight1 Por m~st~purpo~e~ T8A~or;~TBE in~the:amount of 0~.5~ of the inter~al-combustion:fuel by weight~mixed ..
with MEg in the amount of 2.5% or 3% of the internal~

,., ,~ .

~9~/lX116 PCT/~Z~3/00012 combustion engine fuel by weight provides sufficient ~:
improvement in performance of the internal-combustion engine fuel.
It should be emphasized that while MEK i~ an effective additive for hydrocarbon without MTBE or TBA
it is not as eff~ctive.

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Claims (34)

WHAT WE CLAIM IS:

1. Fortified hydrocarbon comprising a mixture of a major portion by weight of hydrocarbon base and as an additive a minor portion by weight of MEK together with TBA and/or with MTBE.

2. Fortified hydrocarbon comprising a mixture of a major portion by weight of hydrobarbon base and as an additive a minor portion by weight of MEK and MTBE.

3. Fortified hydrocarbon comprising a mixture of a major portion by weight of hydrocarbon base and as an additive a minor portion by weight of MEK and MTBE.

4. The hydrocarbon defined in claim 1, in which the amount of the additive is within the range of 0.5% to 20% of the hydrocarbon base by weight.

5. The hydrocarbon defined in claim 2 or 3, in which the amount of additive is within the range of 0.5% to 10% of the hydrocarbon base by weight.

6. The hydrocarbon defined in any one of the preceding claims, in which the hydrocarbon base is gas.

7. The hydrocarbon defined in claim 6, in which the hydrocarbon is torch gas.;

8. The torch gas defined in claim 7, in which the amount of additive is within the range of 6% to 20% of the hydrocarbon base gas by weight.

9. The torch gas defined in claim 7, in which the amount of additive is within the range of 3% to 13% of the hydrocarbon base gas by weight.

WO 93/18116 PCT/NZ93/000?2

10. The torch gas defined in claim 8, in which the amount of additive is within the range of 10% to 15% of the hydrocarbon base gas by weight.

11. The torch gas defined in claim 9, in which the amount of additive is within the range of 6% to 9% of the hydrocarbon base gas by weight.

12. The torch gas defined in claim 8, in which the additive contains TBA in an amount up to 3% of the hydrocarbon base by weight.

13. The torch gas defined in claim 9, in which the additive includes an amount of MEK from 3% to 10% of the hydrocarbon base by weight and an amount of MTBE from 1 to 3% of the hydrocarbon base by weight.

14. The torch gas defined in claim 8, in which the amount of MEK is about 10% of the hydrocarbon base gas by weight and the amount of TBA is about 2% of the hydrocarbon base gas by weight.

15. The torch gas defined in claim 11, in which the additive includes an amount of MEK from 4% to 6% of the hydrocarbon base by weight and an amount of MTBE from 2%
to 3% of the hydrocarbon base by weight.

16. The torch gas defined in claim 7, in which the base gas is LPG.

17. The hydrocarbon defined in any one of claims 1 to 15, in which the hydrocarbon base is natural gas.

18. The hydrocarbon defined in any one of claim 1 to 15, in which the hydrocarbon base is liquid at ambient temperature.

19. The hydrocarbon defined in claim 18, in which the hydrocarbon base is gasoline.

20. The hydrocarbon defined in claim 18, in which the amount of additive is within the range of 0.5% to 10% of the hydrocarbon base by weight.

21. The hydrocarbon defined in claim 18, in which the amount of additive is within the range of 2% to 5% of the hydrocarbon base by weight.

22. The hydrocarbon defined in claim 18, in which the amount of additive includes an amount of MEK from 2% to 3% of the hydrocarbon base by weight and an amount of MTBE from 1% to 1.5% of the hydrocarbon base by weight.

23. A process of making fortified hydrocarbon which comprises supplying additive including MEK, and MTBE
and/or TBA, and supplying a hydrocarbon base, and mixing the hydrocarbon base with the additive.

24. The process defined in claim 23, including supplying LPG as the hydrocarbon base.

25. The process defined in claim 23 or 24, including supplying additive within the range of 0.5% to 20% of the base hydrocarbon by weight.

26. The process defined in claim 23 or 24, including supplying MEK additive within the range of 5% to 15% of the base hydrocarbon by weight.

27. The process defined in claim 23, 24, 25 or 26, which comprises supplying the MEK additive in conjunction with activated carbon.

28. A process of heating which comprises burning a base hydrocarbon fortified by the addition of MEK, and MTBE
and/or TBA.

29. A process of torch cutting ferrous metal under water which comprises supplying to a torch deeply submerged in water a mixture of oxygen with torch gas fortified by MEK, and MTBE and/or TBA, and cutting the metal using the thus fortified torch gas.

30. The hydrocarbon defined in claim 20, in which the additive contains TBA in an amount up to 2% of the hydrocarbon base by weight.

31. The hydrocarbon defined in claim 21, in which the amount of MEK is about 2.5% of the hydrocarbon base by weight and the amount of TBA is about 0.5% of the hydrocarbon base by weight.

32. A method of operating a combustion engine, in which, as a fuel for the engine, a fortified hydrocarbon as claimed in claim 1 is used.

33. A fortified hydrocarbon substantially as hereinbefore described.

34. A process for producing fortified hydrocarbon substantially as hereinbefore described.