CA1149164A - Combustion of organic amine with hydrogen carrier - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The present invention provides a method of improving the com-bustion of an organic amine having a molecular weight of from about 31 to about 110, which comprises mixing in said amine from 0.5 to 15 percent by weight of a hydrogen carrier, and combusting the resulting mixture; said hydrogen carrier being a compound of hydrogen and at least one element selected from the group consisting of sodium, potassium, magnesium and boron, said compound having a molecular weight of from 8 to about 125, a heat of formation of from about 10 kcal. to about 100 kcal. per mole; provided that the compound selected is non-reactive with the amine it is mixed in at ambient temperatures, does not lower the shelf life of the mixture, does not deteriorate below the ignition temper-ature of said mixture to release energy and at the point of igni-tion, released energy and hydrogen, said mixture being non-hyper-golic.

Description

9~ 6~

The invention relates to novel Euel compositions and their use and more particularly concerns methods of improving the combustion of fuels such as amrnonia, petroleum distillates, al-cohols and amines by release of energy and hydrogen at the time of ignit;on.
This application is a divisional app]ication of copend-ing application No. 280,622 filed June 15, 1977.
It is vital that ne~ sources of high energy fuels be developed and that presently available substandard fuels be im-proved to raise their usefulness and efficiency. Prior hereto,it was appreciated that ammonia, petroleum distillates such as naphtha, benzene and the like, volatile alcohols andamines were fuels which upon combustion form cornbustion gases with considera-bly greater thermal energy than the initial combustion reactants.
~owever, each of the above mentioned fuels has failed to achieve an important commercial position as an energy source. As fuels, ammonia, certain of the petroleum distillates, volatile alcohols and amines have shortcomings which can very generally be said to relate to an unsatisfactory combustion. The reasons for the unsatisfactory combustion are varied and individual to the 6~
particular fuel as will be described in greater detail herein-after.
There is agreement among those who are knowledgeable in the field of energy fuels that hydrogen is the ideal fuel of the future, but that it will be decades before engineering has been developed to meet the practical requirements for utilization of hydrogen per se as a commercially significant fuel. The de-sirability of utilizing hydrogen as a fuel is based on three factors. First, hydrogen can be produced in abundance from abundant and inexpensive raw materialsO Second, as a source of energy, hydrogen provides 61,000 BTU/pound upon combustion and third, the product of hydrogen combustion is water, which poses no pollution threat to the ecology.
To enhance the combustion of a number of conventional fuels and fuels of poor combustibility, it has been previously suggested to add gaseous hydrogen to the combustion mixture.
The addition of hydrogen or combustion mixtures can provide ad-ditional thermal energy release, lower ignition temperatures, advance flame speeds, reduce the undesirable emissions of nitro-gen oxides and carbon monoxide and generally effect a more ef-ficient combustion. However, the previouslv proposed methods of adding hydrogen to comhustion mixtures have consisted of ad- -ding gaseous hydrogen to the volatilized fuel at the time f `~1 ~ g~
o ignition or just prior thercto; ~ee or example ~. S.
Patent RE 2~,547 The systems ~roposed l-ere~ofo~e for injecting gaseous hydro~en into a comJ~ustion mixture have, been complex, costly and of questionable reliability. Xn ; general, tlle prior sy6tems have required such thlngs as a ' ~eparate hydrogen injection ~ystem, including dual fuel supply lines; provision for ~eneration and/or storage o~
hydrogen ~as and new carbure~ion con~rol sy3tems and like . compllcated ap~aratus. ~s o this time, no co~ne~cial .
) ll~drogen ~as u~ilizing sys~cm has heen available because o the technical problems invo~.v~d in meeting these requirements.
~y tlle method of my invention, hydrogen is made available to the combustlon mi~ure by dissolving a hydrogen carrier in the base fuel to obtain novel uel com~ositions.
The carrier L-eleases hydrogen for combustion at the time of ignition and thus obviates the need ~ox a separate hydrogen ~as injection system, dual fu~l supply system, special carburetion devices, fuel mixing controls and hydrogen gas re-leasing ~ generating and storage eq~ipment The fuel O compositions of my invention are also advantageous in that the h~drogen carrier employed is a chemical compound which has chemicall~ bound hydrogen The release of llydrogen from the carrier occurs when the chemical bond is broken with a conse ent release cf energy. This energy release s-rves as Il I
~ 4 -. . .' .

.,1~ , ~ 6~
an "ener~y kick" to a~sist ignitioll and boo~ co~u~tion of tlle base fuel and the aclditive, Xt was previously ~ppreciated th~t ammonia in .
admixturo wi~h air forms an explosive fuel mixture which can operate internal con~ustion engines. ~iowever, ammonia -has be~n consldered inferior to hydrocarbons as a ~uei ~ecause it has a relatively l~igh ig~kion tcmperature in admixture with a.ir, i.e~; on the ordcr of about 780C.
Furtllermore, the ~xplosive range of amlnonia and air mixture ls quite narrow, i..e.; within a range of cibout 16 to ~5% by weight of anh~drous ammonia in admi~ture wi-h air. This requires sensitive carburetors. Also the lligher temperatures re~uire different all.oys and designs ~or the engine.
Illustrative of priox art attempts to obtain a satisfactory fu~l composition based on ammonia is U. S.
Patent No. 2,559,605 which discloses the addition o an auxiliary gas to prime the explosion of a mixture of air ' and ammonia. Representative of the auxiliary gases disclosed .
are hydrocarbon gases, carbon monoxide, methanol vapors, methylether, eth~lether~ methylamine, ethylamine or a mixture of su~h gases. In U. S~ Patent No. 2,393,594 an attempt was made to upgrade ammonia as a fuel or use in.internal combustion engines by dissolving a~monium nitrate ~as an oxidlzer) in.llquid ammonia. The latter patent also discloses . ,. . , . ~ 5 _ -. .'~'~

- _ _ fuel m~xtures o ~mmonla and low molecular weight ~lcohols with ammonium nitrat~ dis,solved ther~in. ~noth~r approac~
is representecl by U~ S. Patent No. 2,140,254 which discloses a device em~loyil~g fuel mix~ures for internal combus~ion engincs compl^isillg mixtures of ammonia with h~drogcn gas and nitrogen gas. Other appxoaches to the use of ar~onia a~
a fuel have included its admixture with hydrocarbon fuels ~or use i~ internal con~uskion engines ~see for example U, S~
Patent Nos. 1,5~9l885; 1,671,158; and 3,150,645). Compositio~s of ~nmonia and at least 30~0 by weight of lithium ~orohydride are disclosed in U. S. Patent 3,108,431 as rocket fuelB, ~e. î
fuels possessing hypergolicity.
Although it was previously known that certain boro-hydrides formed mono, di, tri and tetra-ammoniates (U. S.
Patent No. 3,108,~31) and that certain boron compounds were advantageously used in admixture with liquid hydrocarbon fuels (see for example U. S. Paten~ Nos. 3,738,81~; 3,403~014, 3,215,740) it was not heretofore appreciated t~at minor proportions of these compounds could ~e employed to prime and enhance the co~bus~ion of ammonia-air mixtures.
In general, all o the prior art compositions and methods of employing ammonia as a fuel have not been entirely satisfactory for a number o~ reasons, such as, or example, the dificulty in employing a relatively pure ammonia and ,1 . '.
. ,.'.

, ~ 6 ~

. , . ' . ' '`;~

,(. 11 .
~ 64 o~aining thc ncce6sary high initial l-eat flash to b~ing about an ~uto-i~nltion. No commercial application ever re6ulted from such attempts, Tlle improvements of pctroleum distillates such as gasoline as a f-lel, by the addition o rom A to 10% by weight of hydrogen gas to the vapor~ o~ ga601ine has becn suggested; 6ee, for cxample, Chemical and Enginee~ing News, ~pril 14, ]975, page 19. The benefit~ 6uggested include a xeduction of nitrogen oxide emissions and carbon monoxide , emissions due to the lower ignition temperaturès associated with the mixtures. However, as discussed above, the dificulty of using hydrogen gas hereto~ore or its fuel potential, particularly as a motor fuel resides in the engineering problems o storing, transporting and adapting it to the automobile engine. The6e difficulties are overcome by the method o~ my invention. The add7tion of ammonia to improve hydrocarbon uels is dis~losed in U. S. patents Nos.
1,589,885 and 1,671,158, :
Quaternar~ ammonium borohydrides are disclosed in U. S.
Patent No. 3,403,014 as useul when added to high volatility gasoline (Reid vapor pressure above ~) in propoxtions of from ;
0.001 to 0.1% by weight of the gasoline, as a,cold weather anti-stalling additive.
Current interest in substitutes fo~ petroleum based fuels has included the lower molecular weight~ volatile ~ `` _ 7 _ : `,`' . . .<,,.,~
. '.
.. _ ... ___. .... _ _ . . _ _ . . , .. . ~ .. ~ . ...

~4~
alcohols such a6 me~ nol, e~hanol and t-but~nol which ca~
~e ~ynthesiz~d without resort to pe~roleum starting material~
Methanol has been tlloroughl~ studied as a fuel (see for example Reed et al., Science 1~2, No 4119, page 1299), ~he advantage of using me-~hanoL as a hase uel is related to it~ ';
hig~ octane ratlng, th~ lower combustion temperatures with i consequent lower exhaust temperatures, lower emisslons of '~
nitrogen oxides-and improved combustion o mixtures of `
gasoline with up to 15% by weight of methanol. ' The~e are, Ilowever, disadvantages associa~ed wlth the use of methanol, alone or in admixture wi~h gasoline as a fuel. For example, mekhallol may require heating to volatil;ze~
~n addition, methanol has a low flame speed, corrodes engine parts (through aldehyde and acid formation) and lowers mileage per gallon (by a factor of 0.5) because of its lower energy value (in comparison to gasoline). By the method of my invention, methanol as a fuel'may be upgraded in that comhustion efficiency i~ lmproved, flame speed'i~ increased, j;
corrosion lnhibited and the mile~ per gallon ratio improved.

s-lmmarY of khe Invention ;

The invention comprises a method o improving the~
comhustion'of a bas~ fuel select~d from the group consistlng of ~mmonia,-petroleum distillates, alcohols h~ving 1 to 16 - 8 - . ' . . '~
. -. ~.. ... .. ~ .
, i (Il,, .
~93~
caL-~on ntoms, in~lusive nnd a molc~llar WCi~llt of ~rom 17 ~o 275 and o.~nic ~min~s having ~ mo]ecular weigllt o~ ~om .~bou~
17 to a~out 110, ~hi.ch compxises; mixing in said base fuel from 0.5 to 15% ~ weight o R hydl^ogen carrier and co~busting the xesulting mixture; said ~Iydrogen carrie.r being a compound o hyaîogen and ak least one element selec~ed from ~he group consisting of litllium, sodium/ potassium, magnesium, borong aluminum and nitrogen~ said compound having a molecular weight of rom 8 ~o al~out 125, a l~eak o ormation o from abou~ 10 kcal. to a~ou-t 100 kcal. per mole ~d compatlbility with the ba~e uel selected, at ambient temperature~.
The term "ambient temperatures" as used ~erein means a temperature within the range of ~bout mînu~ 20F .to about-250~. -The invention also comprises novel fuel compositionswhich comprise from 0 5% ~o 15/~ by weight of a compound of hydro-gen and one or more element~ selected from the group consisting o lithium, sodium, po~assiumj aluminum, magnesium, boron and nitrogen, said compound having a molecular weight of rom 8 ~o 125 and a ~lea~ of forma~ion of rom about ~0 kcal. to about 100 kcal. per mole, mixed in a base fuel selec~ed from ~he group consisting o ammonia, petroleum distillates, alcohols having from 1 to 16 carbon atoms, inclusive and a molecula~ weigh~

. 9 ., .~ ''.

. . ..
, ' ' ';'- .

. . ~ . _ .,' . : ' - . -' . r ( , 1 o~ from 3~ to ~hollt 275 and organic amines having a molecular weight of rom 31 to about llO; provided that ; the compound selected is non reactive with the ba6e fuel . lt is mixed in at ar~ient t~mperatures,does~ not lower S the shelf life of tlle }~ase fuel, does not de~eriorate . below tlle ignition temperature o~ sRid fuel composition to release energy and at the point o i.gnition, releases energy and h~drogen, said fuel composition being non-hypexgolic.
.0 . . The term "non-hypergolic" is used he-.ein i.n its usual sense as meani.ng the composition is not ordinarily . .
spontaneously combustible, when in contact with an oxidizer The composition~ of the invention are particularly . useful fuels for internal comhu~tion engines, turbine . . .
.5 engines, turbine jet engines and for com~ustion in conventional space heating apparatus;
. ,, ,., , ,, , , Detailed ~escription of the Invention . _ . ',' " . ~ . ~

The method of the invention ~s carried out by first mixing from 0.5 to 15% by we~ght of the hydrogen carrier in O the selected liquid base fueIJ Mixing may be effected by .
bringing the components o the novel composit.ion togethex .
a~ ambient temperatures and admixing with the aid of . conventional and appropriate mixins equipment. ~he novel : ' .
' . , , ' ~ ' '-;.

' ' `--'''' 10 ' ' , ,3~,,, _ L~ c . - ~
. ~

( Ij , . .1 ~ ~9~ ~
fuel compos~tions so obt~in~d are t~len i~nitcd in conven~io~al furnaces, internal cornbustion en~ines, turbine en~lnes and like energy utilizing apparatus appropr.iate ~or ~he desire~
combustion and use o ~he fu~l con~positiona~
S Tlle ~ase ~uels e~ployed in the method o the invention are well known material~ characteriæed in part a~ uids which are largely volatile at a~bient temperatures. More .
part~cula~ly, ammonia ma~ be employed in its li~uid form as a ba~e fuel or in combination wi~h the other fuels such as ' Q alcohols, amines and/or hydrocarbons in the ~ethod of the invention~ similarly, saturat,ed and unsaturated alcohols ha~ing from 1 to 16 carbon atoms, inclusive, ma~ be used as base fuels. Such alcohols are well known, and may be illustrated by the aliphatic alcohols such as methanol, ethanol, S n-propanol, isopropanol-, n-butanol, t-butanol, n-pentanol, isopentanol, hexanol, heptanol, octanol, decanol, hexadecanol and the like.. The cycloaliphatic alcohols such as cyclohexanol ma~ also be employed. Unsaturated aliphatic alcohols such as l-buten-4-ol, and the like are alxo xepresentative o~ ;
0 useful base uels employed in the ~ethod o the invention It iB realized that many chemical compou~ds falling ;
within the classifications stated are useful but only a limited number possesses economical ~irtueO
. ,'. - ' ",-,,'-', ' .
. , ',' ' ' '' ',.
~' . . .-' ~ rl .
~ _ PetroJ.eum distillate base fuels are deI'ined as the products of fractional distillation of petroleum ~nd include for example petroleum etller (the pen~ane-hexane-heptane low boi.ling mixtuxe); gasoline ~the hep~ane to dode-cane m.ixtuxe); kerosene tth~ decanc to hexad~calle mixture~
(to 16 carbons) benzcne! naphtha, toluens, n-hexane and l;ke distillates (the kerosenes and addi~ives rnost useful for jet engincs).
organic amines which may be employed as base uel~
!Q in the method o the invention are represented by methy1-amine, dimethylamine, diethylamine, txieth~lamine, aniline, cyclo}lex~lamille, and the ].ike.
Preferred as the base fuel according to the invention are ammonia, certain low~r aliphatic amines (see above) !5 and aliphatic alcohols, particularly ,me~hanol, eth&nol and t-butyl alcohol, by themselves, in mi~turls o~ ~ese with ~r without hydrocarbon admixtures~
The hydrogen carriers employed a~ com~onents o~ the ;!
compositions o the invention ~ay be characterized as organi~ ;
!O and inorganic compounds having a high energy content, i e.;
a positive heat of' ~ormation o~ from 10 kcal. to abou~ 100 kcal. per mole and a~e combustible~ In addition, the hydxogen carriers employed are soluble or misclble (emuls;fi,~le) In the base fuels wi~h which the~ are combined, ., ' ' ' ' '' ,. :, . , ~ ' ' , .
.. . .. ~
- 12 ~ ~ ~

_.. .
_ ~ 6~
at ambient ~mper~tures. Thoso ~k~llcd in t~le a~t will appreciake that the hydro~en carrierS selected or compounding with a particular base fuel must also ~o iner~ in respeck to chemical reaction therewith unde~ ordinary and amblent ' temperature conditions. By inert, we mean tliat the hydrogen , carriers are 6table and non-xeactive wikh ~he base fu~l under ordinary storage condi~ions and do not adversely aec~ the s~lel-life of the base fuel. The hydrogen carxiex ~u~
release it6 energy and decompose at or just under the lQ ignition temperature o~ the compo6itions of the invention so that energy and hydrogen are released fox combu~tion at the time o~ ignition. The hydrogen carrier must be carefully selected to rneet tho conditions outlined above, fox each particular base fuel to be compounded therewikh.
mmonia as Base Fuel -The prefexred ammonia based fuel compositions o~ the invention may be prepared by admixture of liquid ammonia with a hyarogen carrier compound. Preferred hydro~en carriers to be added to ammonia fuel are those selected from a boron hydride, ;
a borohydrideg a hydrazine including a lower aliphatic or aromatic,by ~hemselves ox ~ combination with each other . in the proportions set forth above.~ Admixture of the fuel composition components i~ conveniently carried out at a~bien~
~emperatures employing conventional equipmen~. ~lthough - i3 ~ -I I

` ~9~6~
. thc ammonia component may be admix~d in its gas~ou~ form,.',' ., , .
the admixture iB pxe~erabl~ carx.~ed ou~ with ammoni~ in its ll~uid state under refrigeration and/or super~atmo~pheric pres6ure, Prefexably anhyflrous ammonia is used as t~le base ~uel. ~lso,. ammonia dissolved.in an organic solvellt which per ~e i~ a combu~t-~].e material.
- Any ~oron or borohydri.de compound may be employed as a hydrogen carrier com~onent o the ammonia ~ase uel composition o~ the invention, which i~ cllaracterized b~ its ability to release energy and be oxidiæed readily, Repr~sentative o~ boron and borohydrides employed in p~epari~g the ammonia base fuel compositions o the invention are organic and inorganic ~oxon hydrides ~uch ~g, ~ox example9 diborane, pentaborane, borazine, borazol and inorganic borohydride~
metal borohydrides ~uch a~ lithium borohydride, lithium cyanoborohy~ride, aluminum borohyride, and the like; adduct6 of metal borohydrides and oxganic polynitrogen compounds !.
such as those disclosed ~n U fi. Patent No. 3,.342,814 and having the formula: .

~ . ~M(BHa~X ]~ . - .' - (II) .

where~n L is an organic nitro~en compound composed ~olel~
of carbon hydrogen and nitrogen atom~, said organic nitrogen compound containing at least 1 nitrogen atom coordinatel~
. .
.' ' ' '. ' ' ''. '`
~ 14 ~ . ~

~ 9~L~4 honded to M where M repr~ents alu~linum; wlierein x is ths ~alence o~ M and wherein N i~ a~ into~e~ hav.ipg a minimum ' ,, .
value of l and B maximum value no greater than the number ' .
. P ni~rogen atoms colltained in the organic nitrogen compound 3 L which ~unction a~ Lewis base~; with ~he pro~iso that when M . ' .
i9 alumlnum then ~ cannot be R2NZ'wherein ~ac~ R i9 a ' . monovalent saturated hydrocarbon radical, and whereln Z'ls , hydro,gen or a monovalent satu~ated hydrocarbon radica~, Organic ~oroh~drides suc~ as sodium'~riethylbo~ohydride, ~
~odium trimetllo~yborohydxide, cetyltrimethylammoni~mborohydridet tetraethylaminoniun~borohydride, tricaprylmethylar~unoplu~T~orohydrid , . tripllenylphosphineborane.and the like hydrazonium borohydrides , such as those disclosed in US. Patent No, ~,215,740 and having the general formula: - ,.

S ¦ ~ ' [ ~ [ BH4 ]
! . R"' R""' , - ~ -. ' ., .' ' . . ''.
wherein Rl, R~o and R"' are ~lkyl and R"'~ and R'~n ~re the ,,-same or different and a~e ~elected from the clas~ consisting.
~ of hydrogen and alkyl; and ~ike hydrazonium borohydrides. ' -.
;~ Hydrazine compounds employed as hydrogen carrierq ~n ~:0 the preparation o~ a~nonia ba,se fuel composi.tions are .' .' - . ,'' ' ' ' ' ,,-' .. , .~ ,, , "
. ' . , ', , .~ .

1~
xcpxe6ented ~ hydra~ine, monoalkyl ~ubstituted hyd~azine~ -' such as monomethylhydraziné and the l~ke; un~ymmetrical .
dialkylhydrazines ~uch a~ un6ymmetxical dimethylhydrazine :. .
. ani~ the like; symmetr~cal dial.kylhydrazine~ 6uch a6 for . example ~ymmetrical diethylhydxazine~ ~rialh~ ~stituted . .
hydrazines such as for example trlmethylhydrazlne and .
~etL~aalkyl substitu~ed hydrazines 6uch as for example, .
tetramethylhydrazine~ aromatic hydrazines ~uch as phenyl~ ;.
hydrazine and khe like, . ~ -.
.0 Representative o~ other hy~.rogen ca~ie~s ~hich may ba compounded with ammonia to provide compositions o the . :
.: invention are sodium amide, potassium amide, boronhydride, .
lithium borohydride, ~odium borohydride and the ~ike......... ....
.Pr~erred hydrogen carriers ln the methoA of the .
invention and for ammonia based fuel composition~ ~e the compounds wherein the element compounded with hydrogen i~ ..
. . one or more o.f lithium, sodium, potassium, boron or nitrogen~ ..
. . ~xemplary of ~uch hydrogen carrier~ are~
: . (a) hydroxylamine~ - `-~o ~) iminoalcohols, like N~(2-hydroxy-ethyl) - :
ethyl e lmine.

~: ' ' '', , ' `
:' .. . ........................ . -.
. , ''' " " ' ' ' ' ' , ' ' ' ` ` '' '`"' " :
. , ~

~ 9~
. (c) hydrazin~s i.ncluding alkyl ~uh3titutecl ; hydrazin~s as rep~e~ented by hydr~in~; hydrazlne h~drate, methylhydrazine, symmetrical di.mothylhydraz.tnq, unsymmetxlcal dime-thylhydxazine, phenylllydrazin~3, butylhydrazine, `
S hex~ ydrazine and the ~iko; ' .
~ bo~anes such as diborane, pentaborane/ borazilla and the like;
. (e) borohydrides such as lithium borohydride, magnesium borohydrida and the like;
(~) borane-amine complexes ~uch as boxane~tert- -butylamine, borane dimethylamlne, borane t triethy~amine, borane trimethylamine~ borane , ~yridine, ammonia hydrazine, . decaborane adduct (U. S, Patent 3,291,662), hydrazine -. diborane 3,323,878), hydrazine , tetraborane, ~ydraæine ~on~aborane, trlhydrazine decaborane, dimonomethylhydrazine ~
pentaborane, trlmonomethy~hydrazine ~ pentaborane, ~ethylhydraz-. ine ~ decaborane, dimethylhydxa~ine ~ decaborane, hydrazine~
bis-borane, hydrazino-bis~borane, dimethylhydrazine-bis~
. borane (U. S. patent 3,450,638), diammoniate diborane (U. S. Patent 3,576,609) and the like;
:. (g) h~drazinoalkanols such as ~hydrazinoethano~
~nd the like; and ~ .
(h) borohydride-ammonia adducts such as lithl~
. borohydride monoammoniate (U. S, Patent 3,108,431~ and 25tho like.' ~
. . ' ' ' ' ' ' '" ' -' . ~ 17 ~
. , . ,' . ' `~
. . . . . . - ~ - -; _ etLoloum nisti~la~ ~ nasc ~uel In genexal, the p~troleum distillate ~a6e fuel~
: may ~e im~rovcd b~ ~he me~h~d of the inven~ion by admix~ng - one or more o~ the same hydrogen carrier~ describe~ above S in relation ~o ammonia as a bas~ fuel, Preer~ed as ~he hydrogen carrie~a in ~dmixture With pe~roleum diatilla~eB
a~e hyarazines, especlally alkyl hyArazine~ 6uch a~
unsymmetrical dimethylhydrazine, boron-hydrogen adducts like ~amine~ BH3 ox higheL homolo~les, one o~ the ~igniflcant impxovements resulting from the presence of the additives , deqcribed herein rel~tes to 6ignifican~ reduction o~
undesirable em;ssion components. Also combustion efficiency 1~ increased. .
~lcohols as a Base Fuel ~lS Those skilled in the art will appreciate that the reactivity of alcohols with ~abile hydrogen limit~ the addltive hydrogen carrier-components ~hich may be com~ounded with ~hemO In general, ~he carrier compounds described above ;;
in relation to the improvement of ammonia as a ~se fuel may ~0 be used, pxovided they are non-reactive with the alco~?ol~
Representative o~ preferred hydrogen carrie~ employed as components of the novel composition~ o~ the invention employing alcohols as a base fuèl Rre the hydra~ines described in group (c) above and the borane~amine complexes described in (~) above, proyided they are non-Xeactive with the alcohol and with water.
. ', ,._."~, '. . . , .
~ 18 -. .

. . , .. i.

. ~ ~
Organic Amines as the Base Fuel A broad range of hydrogen carrier compounds may be admixed with organic amine base fuels to improve their combustion.
In general, all of the aforementioned carrier compounds may be used. Preferred carriers for admixture with organic amine base fuels are the boronhydrides EgrouP (e) above~, the hydrazines [group (c) above] and the borane . aminecomplexes [group (f) above).

... .
-The base fuels described above may also be used in ad-~mixture with one another. For example, ammonia maybe dissolved 10 in the amine fuel and serve as a solvent for the hydrogen carrier ~hich in this case advantageously may be represented by unsym-metrical dimethyl hydrazine or one of the amine-borane adducts.
As a furtller example, kerosene and an amine fuel such as -triethyl amine may be admixed with an amine - BH3 adduct as the hydrogen carrier such as, for example, an amineborohydride aduct (amine-borane) as a hydrogen carrier. A preferred hydrogen carrier for .
use in such a mixture of base fuels is the adduct of equimolar proportions of ammonia and one-half B2H6: (NH3 . BH3) or a methylamine or ethylamine - BH3 adduct; i.e.; CH3NH2 . BH3;

(C H ) NH2 ~ BH3; (C2HS)2 NH BH3; (C2H5)3 3 ponding hydrazine adducts like (CH)2 NNH2 BH3.

,, .

.,, , ., ~ ~

. .
.

( 11 ' .;

In a pL^e~errecl c~od.imont of the inven~ion, ~he hydroyen carrier i~ a hy~rate such as, for e~ampleg hydrazino hydrate (N2~50H) or ~ h~rdxazino alcoho~. In !;:
t.his manner, oxygen as well as steam are contri~uted to the ign.ition and combustion process~
In ano~hex prc~ex-r~d elr~odlmen~ o~ the invention, the hydrogen carrier i6 an amlno~alcohol, like N-hydroxy- .
ethyl-ethylene im.ine~ Such novel compositlons have the f~rtller advantage of lmproving combustion e~icIency and lower.ing the emi~sion of noxious by-products~
. Tlle base fuels described above may also be used in admixture with one another. For examp].e, a~monia may be .-dissolved in methanol and both ~ay ~erve as ~olven~ for the hy~rogen carrier which in this case advantageously ~ay be xepresented by unsymmetrical dimethyl ~ydrazi~e, or a ~ta~le amlnoborane t"stable" mea~in~ unreactive or very slowly reactive with.the alco~ol ~ase ~uel. i~ the pa~ticular ~i.xture of alcohol and ammonia employed), As a fur~her example~
kerosene and an amine.fuel ~uch a~ triethylamino~ hydrogen carriers such ~s, fo~ example, an aminoborane adduct as a hydrQgen carrier. A prefe.r~^ed hydrogen carrier for US9 in such a mixture o~ base ~u~ls is the adduct o~ e~uimolar propor~ions of ammonia and boronhydride~

20 - !

. . ~ ,,.
'. ' . , '' .' , ' '`'~ .

`~ ~ ~

In addition to ~h~ h~dL-ogcn C~.~L-ier~ the compos;.~ion~
;: of the invention ma~ also contairl othex additive~ h~ving .
6pecific desired unctions. For exampLe, combu~tion depo~
modifiers such as clà~s may be added to the compositions o~
the invent}on ~nti~oxidants, metal deactivators, corxosion .
inhibltor~, anti-icing agents, de~ergent3, dye~ bricants :
and ~ike conventlonal fuel additives may be added to the uel .. compositions of the invention in conven~iona L proportions to Qffect their particulax purposes upon combus~ion of tho ' O composition of the invention.......................... .
. The compositions of the i.nvention may ~e combusted in conventional combustion equipmcnt ox the equlpment ma~ be modified to meet the special properties of an individual : ? composition to obtain maximum efficiency/ i e ~ compression LS ~atios, cycle timing, air mixtures, pump means for controlling the ~low o~ fuel, combustion timing ~echanisms, and like . control device3 may be modified to meet the ~peci~ic . combustion characteristics o~ the fuel~ provided by the .
method of this invention Tho~e skilled in the art will

2~ appreciate how t~ effect the desired and advantayeous . ~odifications when ~equired for ~aximum fuel eficie~cy~
The ammoni.a and alcohol based fuels are paxticularly advantageous fuels for tur~ine and i~ternal combustion enginesO For example, the alcohol and ammon.ia based fuel . compositions of the invcntion may be employed in internal .' ,. . . . . .
,, ' ,~

_ 21 ~ i . ~9~64 comhu~tion en~in~s using apparatu3 and tcct~nlques ~reviou~ly known? Illustrativ~l~, the coJnposi~ions o khe invention may be storcd and delivered to carbure~or o~ the inkernal co~bustion en~ine described ln U. s. Pa~ent ~o. 2,559,605.
The liquid rnixture~ upon reaclling the carburetor nre volatllized and admixed wi~h air be~ore bcing drawn ln~o the eombustion chambers o the engine. Althouyh it ls preferred that the mixture of ammonia based fuel with air be in ~uch proportio~s as to provide ~rom about ~.5 to about 30% by we~ght of am~lonia, ot~ler proportions may be emp~oyed outside of this pre~erred range. Similarly, a wide range r~ of compression~ are usable in combusting ~he ammonia based compositlons of the invention when mixed with alr.
- ~hen the base fuel i6 an alcohol such as methanol, } 5 the compositions o~ the inventio~ are admixed with air or combustion (ater volatil~at~on), The compressions usable .
. in combusting .the methanol ~ased compositions of the invention are within the normal and known compressions for methanol u~ed pex se. (Methanol responds well to highest compression ratios~.
i The petxoleum distillates and orgal~c amines may 'r' , similarly be employed as fuels in conventional and known equipment for combusting such fuels withou~ major modifications~
The ~ollowing examples describe the manner and process o~ making and using the invention and ~e~ fo~th the ~, ', .,''' '' ' ''~'' ' ' . .
.,,., . '~`` ' .

~. ~ .
,. .. .. ... ... _ . _ . .. _ _ ~ _ . i c~ .

.

~9~64 be~t mode contcmplated by the invenkor o~ carrying out the invention bu~ are not to be construed as limitin~.
: . ~ . , . . ' : , E~ampie 1 ` ` `
,,,: , , ' ' ' ' , ,, . .
A suitable pressure reaction vessel is charged with 100 lbs. of liquid ammonia. To this charge ther~
is added with fitirring 1 lb. o~ lithium borohydride.
The ~esulting mixture i6 stirred for ahout 15 minutes and then t~-ansferred to a pxessure contalner where the li~uid ~ixture is maintained~ The resulting fuel is useful to power turbine engines. Similarly, ~epeating the above procedure but replacing tlle lithium borohydride as emplo~ed therein with an equal proportion o~ a~y other hydrogen carrier compound suitable ~or compounding wikh ammonia as described ~xeviously, a composikion of the lnvention is obtained.
`. . , ' ' '' ,' ' ' .. ~
Example 2 '', ~ .' ` `-`'~
A suitable reackion vessel is charged ~ith 100 lbs.
o~ methanol, ~o thi~ charge there is added with ~ixing

3 lbs. of unsymmetrical dimethylhydrazine. ~he resulting mixture is a fuel which may be used in internal combustion en~ines. Similarly, repeating the above procedure ~uk . '' ,~
`.'. " ' , . . .
~ ~ .- 23 . ;. .
. ' ' ~ ~
,: ' 6~ .
replacing -~lle U~ s u~ed thcrein with any other llyarogcn ;
caxrier previou~l~ descrlbed a~ ~uit~le fox admlxture ' with an alcol~oL, a composition o~ the inveneion i~ obtained, E~ample 3 ,;

.f 5 A sui~able vei~sel is charged with 100 lb~; of ke~osene.
To this charge -there is added with ~tirring 5 lbs. of l~~drazina base. The resulting ~uel may be used i~ a kerosene burning heatin~ plant. Similarly, ~ollowing the above proccdure bu~ mixing in place of the hydrazine base any other hydrogen carrier described above as 6uitab1e for mixture with a ~etrol~um distillate, compositi~ns of the invention a~e obtained, - Ex~mple 4 A suitabIe vessel i6 charged with ~00 ~bs. o~
dimethylamine. To the charge there i~ added with mixing

4 lbs. of unsymmetrical dimethylhydrazine (UDMH~. The s resul~ing fuel may be used to power heatin~ plants, Simila~ly, following the above procedure but replacing the UDMH as used therein with any other hydrogen carrier described above as seful for mixture with an amine uel~ a composition o~ the invention is obtained.
.', . . .1 .. .'.~ '` ' `"i ., ~ - 2~ _ ~
. ' '` ' ' ,.`,~.
. . ,' ' ' ' ' ' ~ ~ i , .. . _ __ _ _ _ _ _ ... ..

~: 1 \~
:~ ~
Example 5 ~ ' . ' .'' ~ .
- The pre~sure container prepared in Example l above and containing 99% ~y wclght ammonia w,ith 1%
by ~l~ight o lithium borohydride is attached to ~
pres~ure reducing valve pxeviously connected to an air mixing burner. The valva is opened to permi~ ' the fuel compo~ition to enter the b~rnex hoad and to be admixed with air in the ratio o about 75 to 25 parts o air to the ~uel composltioh~ The air O fuel compo~itio~ i9 ignited and found to ~urn evenly with a bright yellow flame.
' ' . :
Example 6 .' . ' , ' :
~ Following the general procedures outlined in ! . Examples 1-4, inclusi.ve, additional ~uel composition~
of th nvent~on may be prep.~ed as follows~

- ~
'' ' ."' ..' ' '. ' '' ',.
:' . ' . ,~
' ' ' , '~;
'i . ' , '' ' ',~,, 7"'' ~1. .' ' . ' .,~,.

~ ~9~

pl O D ~ + ~ ~ D
W ~ N .
W W (D ~ (D N ~ ~-,, O ~ (D (1) ,, p) (D D~
~, . O . ~ I I ~ I ~--o O Ul ~ ~ O
I_ ~n ~7 W W W W W ~--~n ~3~
'' o , , , , I ~ 1- ~ ~
U~ n ~ n . . o o~
W W ~ N ~ I-- W 1~) ~] Z
lUl I N~1~rl ~::1 ~ ~ m . . . I . I . I ~--~ W
~n ul ~~ ul wul ~ ~n (D P.
o I I r~ r~ ~ W ~
Ul )- ~C ~3 (PDI ~ ~ ,tnz : , -- ~n ~3 Ul I I I I N ~~1 ~ ~ O
o o o 1 w ~ r~ O
t- I ~ ~
OUl 1--1--~n , 1 1 1 I N 1- 1 oP) O
o O O l ~ 1- ~I P
I I I C~ Ul ~ ~
(Do\

o u~ ~0 O o w r~

~.~
w w ~ ~ w ~ ~ ~- 0 ul Vl ~J7 ~ ul ul ~ r~
Ul Ul ~ W ~ 1-- ~ n 1-- U~ Ul ~n U~ ~; cn n _ I

..

, 9~

lL ~ tlle al70ve fuel c7m,70sitions may be use~ a~ cnergy fuels in conven~ion~l en~ir es, t:urbines and li ~nercJ; l~el ~onsumin~ a 7vic 7s.

!'~ :

~' :~, ,, ' ' ' ' ' , ' ' ';" ' ' ,` . ,' ' ' ~ .

27~, ~

, :, . ., . _ . . ... _ . .. , ...... _ _ _

Claims (16)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method of improving the combustion of an organic amine having a molecular weight of from about 31 to about 110, which comprises; mixing in said amine from 0.5 to 15 percent by weight of a hydrogen carrier; and combusting the resulting mixture; said hydrogen carrier being a compound of hydrogen and at least one element selected from the group consisting of sodium, potassium, magnesium and boron, said compound having a molecular weight of from 8 to about 125, a heat of formation of from about 10 kcal. to about 100 kcal. per mole; provided that the compound selected is non-reactive with the amine it is mixed in at ambient temperatures, does not lower the shelf life of the mixture, does not deteriorate below the ignition temp-erature of said mixture to release energy and at the point of ignition, releases energy and hydrogen, said mixture being non-hypergolic.

2. The method of claim 1 wherein said hydrogen carrier is selected from the group consisting of borohydrides, boraneamine complexes and mixtures thereof.

3. A composition, which comprises; from 85 to 99.5 percent by weight of an organic amine having a molecular weight of from about 31 to about 110; and from 0.5 to 15 percent by weight of a hydrogen carrier, said hydrogen carrier being a com-pound of hydrogen and at least one element selected from the group consisting of sodium, potassium, magnesium and boron, said compound having a molecular weight of from 8 to about 125, a heat of formation of from about 10 kcal. to about 100 kcal. per mole; provided that the compound selected is non-reactive with the amine it is mixed in at ambient temperatures, does not lower the shelf life of the composition, does not deteriorate below the ignition temperature of said composition to release energy and at the point of ignition, releases energy and hydrogen, said composition being non-hypergolic.

4. The composition of claim 3, wherein said hydrogen carrier is selected from the group consisting of borohydrides, borane-amine complexes and mixtures thereof.

5. A method of improving the combustion of an organic amine having a molecular weight of from about 31 to about 110, which comprises; mixing in said amine from 0.5 to 15 percent by weight of a hydrogen carrier; and combusting the resulting mixture; said hydrogen carrier being a compound of hydrogen and at least one element selected from the group con-sisting of sodium, potassium, magnesium, nitrogen, and boron, said compound having a molecular weight of from 8 to about 125, a heat of formation of from about 10 kcal. to about 100 kcal. per mole; provided that the compound selected is non-reactive with the amine it is mixed in at ambient temperatures, does not lower the shelf life of the mixture, does not deteri-orate below the ignition temperature of said mixture to release energy and at the point of ignition, releases energy and hydrogen, said mixture being non-hypergolic.

6. The method of claim 5, wherein said hydrogen carrier is an alkyl hydrazine.

7. A composition, which comprises; from 85 to 99.5 percent by weight of an organic amine having a molecular weight of from about 31 to about 110; and from 0.5 to 15 percent by weight of a hydrogen carrier, said hydrogen carrier being a compound of hydrogen and at least one element selected from the group consisting of sodium, potassium, magnesium, nitrogen, and boron, said compound having a molecular weight of from 8 to about 125, a heat of formation of from about 10 kcal. to about 100 kcal. per mole; provided that the compound selected is non-reactive with the amine it is mixed in at ambient temp-eratures, does not lower the shelf life of the composition, does not deteriorate below the ignition temperature of said composition to release energy and at the point of ignition, releases energy and hydrogen, said composition being non-hyper-golic.

8. The composition of claim 7, wherein said hydro-gen carrier is an alkyl hydrazine.

9. The composition of claim 7, in which the hydrogen carrier is a complex compound of nitrogen and boron.

10. The composition of claim 7, in which the hydrogen carrier is hydrazine.

11. A composition of claim 7, in which the hydrogen carrier is an alkyl hydrazine.

12. A composition of claim 7, in which the hydrogen carrier is dimethyl hydrazine.

13. A method as claimed in claim 5, in which the hydrogen carrier is a complex compound of nitrogen and boron.

14. A method as claimed in claim 5, in which the hydrogen carrier is hydrazine.

15. A method as claimed in claim 5, in which the hydrogen carrier is an alkyl hydrazine.

16. A method as claimed in claim 5, in which the hydrogen carrier is dimethyl hydrazine.