DE1645885A1 - Distillate fuel - Google Patents

Description

OR. ELISABETH JUNQ AND DR. VOLKER VOS8IU8

• MONCHfN IS · STIOIMTRAStEM. TELEPHONE MIM7. TELIOIIAMU-AOfIIIiIi INVINT / MONCMIN

P. 5792 Munich, the 26th Sept. 1967

y / s

31L3I.L IUTjSiÜiA'i'IOiiALii RJüiSJiiUlCII MAA3? ÜOHAKPIJ H.V.,

Dan Haag / Holland

_. —_—

¹¹ waste fuel »

Priority: September 28, 1966) July 27, 1967 ] Arunelde no. 43 366/66

The present Srf indune relates to a De atiUatkraf tat off which oicb inebeeonäero for Plugzeugturbinonmotore and al ο Baaißöl contains a KohlenvTassarotofföldoatillat.

la scope of the invention will be a hydrocarbon oil distillate a ül might understand, welcheβ in DoetIllation of crude oil obtained UNOE of which at least 96 vol .- ^ at Atoosphilrendruck and 40O ⁰ C not überdeetillieren excess temperature and welcheB further comprises a Aschecehalt of höchstene 0.01 Gaw .--> u points to.

ü09852 / 1785

Deetillatkroftetoffe tend with aging and especially with Altorn under higher! for the separation of footer precipitates. This fact has a particular disadvantage in the case of flood kerosene, which rubs off in hyperechoic fluids, because fuel for this special purpose does not only last several hours in the temperature range between 100 and 200 ⁰ C but also for shorter periods of time at temperatures "bit to 300 ⁰ C and must Vin higher stable because such high i'enpcraturen may occur when the fuel has to take überachüeai ^ e" poor. the achlammartiren itself or abacheidenden under the ^ inv / irkunc higher temperatures Deiin aging or Featen substances can clog the fuel filter and prevent proper functioning of the surfaces of the urneauotouscher.

Sm has now been found, dioso Kachteile dad corrected, or at least reduce laeoen "when running down the fuel _f; ausetat Erince amounts phoapljorlialticer esterartißer reaction products.

Bor erflndunirc ^ euiiße Deetillatkroftstoff consists of a KohleiiwasserstoJffoldestiilut and a little part neron "! Close a isternrtinen ReakfcionsproduVfcea 1 iiol a connection rt (01f) _» V7obei κ a Kohlonviacaerstoffreet with up to 30 A-oblenstoffatowen and χ a ■ integer over 1 means .0.5 - moles

009852/1785

a carbon / hydrogen-substituted succinic acid at least 50 carbon atoms in carbon substituents or a functional derivative of such a acid and 0.1-10 get a phosphorus-containing sturdy or of a functional i / orivate of such an O acid per I.iol the succinic acid reaction component.

The ßnaioJl preferably consists of a fluckerosine,

which is suitable for the drive of a plug-in turbine engine, a temperature range between 80 and 35O ⁰ C as well as a ™

Ascne content of hüchstena 0.01 Ggw .- ', v aufv.eist.

?. Gemilfl a particular functional ÄusfUhrungsform enthiilt the Dcetillatkraftetoff 0.0001 - 0.05 percent, -i _"t particularly 0.0001 - Of025 Gev · ^ ο and, βάλ special beTortsugt 0.0001 O ₁ Ol weight * -; £ of phosphorus content reaction product.

As Folyhydrohrverbindung the formula Ii (OU) _x for Iferetellunc of estarartlgen Rccktionsproduktcs ince> NEN polyalcohols, especially those nit 2 - 12 carbon atoms and 2 -10, (vorzucBTTsiae 3-6, Hydroxyeruppen Examples include Alkylenßlyoole and lOlyalkylenjlycole, τ.. -ie ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, iributylene glycol, i'entafithylene, glycol and other i'olyoxyalkylene glycol.

Such polyoxyalkylene glycols by condensation of 2 or more molecules of ethylene glycol, propylene glycol, octylene glycol or an analogous ulycol oit bit: su 12 carbon «

009852/1785

Atoms in the Alkyienrest are produced, other suitable ones Polyalcohols are glycerin, fantaeritbrit, 2,4 ~ hexanediol, nnakol (Pinacon), larithritol, arabitol, sorbitol, mannitol, 1,2-cyclohexanediol and 1,2,5-cyclohexane triol.

Al »polyhydroxy compounds can also be polyphenols, 4.B. Hydroquinone and Roeorsln, as well as Uonoeoter are used » e.g. Monoeter clay glycerine, sorbitol or mannitol, such as oleic acid acetate, üorbitiaonooleate and Hannitraonopropionat.

Another internal class of polyhydroxy compounds binds polyhydroxy compounds from an unsaturated alcohol such as allyl alcohol, and a polyhydric compound with an olefin double bond, ** B » styrene, vinyl ether, vinyl acetate , isobutene, butadiene and divinylbonzene»

Koiileimaeaeretoffreet B in the given formula can also be substituted by polar groups Rain, BB, by IaIo eenatoee, provided that the coal wa & oeratoffcharacter of the Omppe is not compromised by such substituents.

AIa Bernateineäure-KeaJttionalconiponente for the Meratelluag The inducers outside phosphorus content can open themselves kobXamvaaaeretoffsubetituierte Berneteinäuren eowia their Anhydrides and halides or

009852/1785

Dor Kohlenvvasseretoffsubstituent mark by polymerizing i onoolefinen "it 2 - 30 carbon atoms are obtained to be" Thus, suitable Kohlenwasaergtoffsubetituentsn poly "ffiorieate of -. Aonoolefinen as ethylene, propylene» »butene" isobutene l-IIexen _e l-octene! 2-Ethyl-> l * »octene, 3- ° Glyclobe5yl-1-butene and 2-ethyl» 5-propyllaesen »Polymers of olefins which have no end and indigo double bond» such as 2-ßutQü, and Mieohpolyrnerisatö can from the aforementioned | Olefins have other olefinically unsaturated ones. Yor bonds » ζ.Ά * olefinic aromatics» such as styrene »cyclic olefins _t such as 1-cyclohexene» and polyolefins as carbon waste hydrogen substituents.

Olefinisabfi l'olyjwre with olecular inequalities in the range from 7 to 5000 are preferred as Koulemraseeratoffeubatlenten of the succinic acid and other functional derivatives, although for this mixture also olefinic polymers with higher

bia s «B» 100 000 used if you can · '

.Such kohlenwaeaeretoffsubatituierten Berneteinaäuren and their derivatives laaoen aich in itself known? Manufacture wise, £ «3. by reaction of a polyolefin or a iualeineäuroanhydrid with Kohlenwaeaerstoffhalogenid at i'eaperaturen in loading rich * 100-200 ⁰ C..

0 0 9852/178 5

• ο ~

A large number of phosphorus-containing? Acids and their derivatives. In addition to the organic and inorganic phosphoric acids and phosphorus acids, their anhydrides, jisters and acid halides can also be used. The term "phosphoric acid" applies not only to the compound H3PO4 but also to sulfur-containing phosphoric acids, i. E. Phosphorothionic acids of the formulas H ₅ PO ₃ S, H ₅ K) ₂ S ₂ , H ₅ POS ₃ and H ₅ Po ₄ . Suitable acids are phonphorhaltige beispielev7üiae alkyl, aryl, alkaryl, aralkyl and Cyclohexylphoaphoraöuren and -phosphorige acids ₈ wherein the hydrocarbyl substituent of up to 30 Kohlonstöffatome sov / ie also polar groups "as Halogenatoste may contain, vorausgeeetat, the hydrocarbon character by such Dafi «Substituents are not affected. As phosphorous ^ fieaktionskorapOBente further PhospborsSureanhydrid., Pohoe "paorpentaaulfId, Phosphoroxyeulfid, anhydrides köauen the aforementioned koblenvraseerstoffeubatituierten. Phosphoric acids and phosphorous acids, phosphorus trichloride, phosphorus pentaofaloride, fboepboroxvchloriäfl diphenylphophosphorus trichloride as well as the completely or partially esterified phosphoric acids and phosphoric acids are used which have a hydrocarbon radical of the type mentioned above. Examples of such hydrocarbon radicals are iiethyl, ethyl, propyl, butyl, isobutyl, octedecyl, stearyl-t oleyl, allyl, phenyl, tolyl, bensyl, heptylphenyl and haphthyl radicals. The hydrocarbon radical can also be derived from polyisobutene

009852/1785

> ■ 7 -

The abovementioned pböüphor-containing iSaters can be silenced using methods known from Bioh. Deiopielav / Gifie one can first bring the polyhydroxy compound to the kohlenwaeeerstoffeubetituiertea succinic acid or its derivatives to neutralization and then uaoetz the product formed with dorophore-containing acid or its derivative. iJine other UÜclichkeit heateht in the reaction of the polyhydroxy compound with the phoophorhaltigen acid or your derivative and the subsequent reaction dee no product obtained nit the kohlcnvraeeoratoffeubetituierten Bernateinaiiuro or derivative thereof, 'continues all three Reaktionapartner is equilateral with © inender uogoaetst v / Ground · üb often BvreckiTi'-iUi ^, the phoaphorhaltlgen Üeter in an inert Luoun ^ esaittal hersuetöllen _f a.i3. when the reaction product containing the itater is very viscous or feet. For this 2 \ veck ceei ^ note solution are! carbon emvasoeretoffe »such as benzene, toluene» cyclohexane and n-ilexane, furthermore jäinoral oils, eg a> 3. indelüldestillat, a light SchiaierOl or a (KeroBin. vlpesielle Heaktionsbedin ^ essen, which I have proven for the production of the pliosphoric iister ala 2V7eckwtLßiß, are described in the British Fatentechrift Ho, 1 054 276 "

The chemical structure of the phosphorus contained in this way

ßster is not yet known exactly, but it seems that there is the connection of an olyhydroxy compound with an amber *

00985 2/17 86

acid or its derivative and a phosphoric acid or its derivative some of the hydroxyl groups with the borne component and other hydroxyl groups old of the PhoaphoroHure component to form a convoluted odor of meters of the polyhydroxy compound; react. If.an can, with a few years of incongruity, evolve some of the formulas formed in the process, the relatively simple structures represented below by the formulas I and II. "

χ I r ι ■ ■

R -CH-CO- IcH ₂ - CHR - Oj - P (OR! «) CH- CO- JcH ₂ - CKR - ά - P (OR ")".

! 0 - 0 - fat, -CHR - Ol ~ P

r ι

OH

OH 0

cn - c - o »| ch « - cm - o \ ~ ρ «Γο-« cm - ciu \ _ oh Ii

Often

52/1 / ÖS

In this form, the unit - ^ ^- CH ₂ -CHR-OJPV means a polyoxyalkylene unit, while the hydrocarbon radicals occurring in succinic acid, in the polyhydroxy compound and in the phosphorus acid are corresponding structural formulas for The simpler JSsfcer readable from other polyhydroxy compounds are set up such ssters contain two phosphor atoms in iAolecule. In the reactions described above, however, esters with more than two phosphorus atoms in mols also form _, which depends on the number of hydroxyl groups which for. The reaction with the phosphorus acid is available, while on the other hand cross-linking results and ring formations also play a role if an aryl phosphite participates in the formation, then in the course of the reaction the eatepreohenic phenol is released and forms the one component of the

Phöspherhaltige jäster of the type described above gives way more than two phosphorus atoms in the molecule are suitable especially good as additives according to the invention

Otnvohl the phosphorus-containing Sster are soluble in hydrocarbon oil distillates and also generally little the cat bow are required * but iat.ee often xweckmä0ig _r the hangover the fuel than Löuung In a U leiohten lubricating oil or any other suitable inert solvent "uauset- 's,

00 9 8 52/1785

In addition to the new additives, invented new distillate fuels can also contain a smaller proportion of a metal * disactivator »wle.N _f U ^l HDiaalloylidin ~ l} 2-propandlaraln«. If necessary, other additives can also be added to the new fuels, such as anti-oxidation, anti-aging, anti-static charging, anti-corrosion agents, chemicals, corrosion inhibitors and / or coloring agents. Such additional additives can be rubbed into the fuel βία lüsvmg »ueaaoan ■ 1t of the ester.

Antioxidants. whose Geeaatkonseetration in the fuel but should leave 24 sg / Xiter »are Z , 6-tertiary-butyI-4-ethylphenol _$ 2,4-diethyl-β» tertiMrbutylptaenol »2» S-diteftiary-buty! phenol'-and cooiochte tertiary butylphenols. * '-''

The tortelle of the present noise finding is tied to one Hoohteaperaturteetea nfiber explains * which the conditions of the sink · »of the Vorwäraern and the filter · naohahat, which one Fuel in a 3 »iiach ~? Location is likely to be exposed -

0098 5 2/1 7 ^ 8 5

"Life is all about a" modified Fora de "aogenaanten OFfi-fuel-Coker-Testa (ASIM JJ 1660), noble a fan ture of 135 ⁰ C, a temperature of the preheater of 223" 9 ° C and a filter temperature of 273.9 ⁰ C instead of the lower temperatures specified in the ASTM standard. In every other respect, the D 1660 is being worked on. In this work regulation ASTA D 1660, the fuel is pumped with a certain flow rate through a Torwäraerabeehnitt and then through a treated filter outlet of the CRP-Puel-HJoker. The stability of the initial offset is then assessed based on the performance of the preheater waste committee (evaluation range 0-4, depending on the length of the precipitate) and the pressure drop (/ \ P na llg) within the filter committee. The pressure drop leads to the formation of song blows in the filter section as a result of the preparation of the oil. iiln for operation einee. 3 -, ROH JPlufeeugae appropriate fuel should have a pressure drop of less than 76 »2 mm Hg and a Kohrbowcrtung ala dea Vorwtiraerabschnittee of less 3, λι hen radio, VorwUraer and tilter a temperature τοη 135 ⁰ C. ber. '. 223.9 ⁰ C bew, 273 "9 * C have"

We üe "a erfinduujBgenfiiler Deetillaikraftetoff hergeetellt and tested <! Sine Polyhydrozyrerblnöung and kcililerwaßeerdarnateinsäure the above bcsechr praise ta Art © in i are riarylphoepiiit? EusBwmen in a leichtea ISI * r I inert" Löeuntaraittel zQßäü άβι \ YoTBtibstt% 9ti <l "r .Vatentachrift No * X ' 054 2? 6 together

009857-17-85

BAD OBJQJNAL

Be is an amount of the Phosphorsäurereaktionakomponente used that aae fteaktioneprodukt a Phoephoreebalt of about 2 i> having the Auecangeraaterialien have a commercial purity agrad and ee been Iceine special measures are taken, mn the Ileaktioneprodufct ku clean _f eondem ee is only dae the phoephorhaltigen Beter containing reaction product aittela dialysis separated from the leiohten Sefamier * ul, jdah bo receives a product »deseen zueammeneet by Analyae v / ie fol ^ 't beatimrat virdi'

Phosphorus content in Qen, -ji 1 »8 Chlorine content in Oew .- *; v 0.32 α e content of strong acidity (tfillisrama KOH / Grama) 5.86 Low acid content " 16.4 Molecular weights 7,000 to 30,000 Medium molecular weight 24 400

Infrared nlyo © dea dialysicrtm materials becomes feat »
™ geetellt that ea carbonyl bonds (Eater bonds) and, Phοβ-phor-oxygen bonds, also Phoaphor-Ghlor bonds,
Fhonphor-Oxygen »& Oblenatoff * 5indunGes and aromatic
Contains bonds · The dialyzed material is then pyrolled in Takuua and the pyrolyte oaeeenepektroi & etrieeh examined. _{As a result, the clay butene, C 6} -01efin, toluene and styrene are given to the suppliers for the pre-flowing clay
Pyrolieateo perkoliart aan through a column

009852/1785 '

Using a 60 / SO ⁰ C Benain, benzene, chloroform and acetone as an isolating agent, the fractions obtained in this way are examined by means of infrared spectroscopy. This gives evidence of the presence of polyisobutene, succinic anhydride, polystyrene, long-chain compounds, and sub-rods or I-boephor-Sauerotoff bonds. From the phosphorus content of the dialysis-based material, you can conclude that the lister or didactic odor contains compounds with an average content of about 14 phosphorus atoms per molecule.

Sas dialyeierte material abgektlrst below al · "P-containing Seter" is called * Wet aaa in a Kohlenwasserst of iölddstillat on (Plus ^^ iin which d9n Under ^Ε · ^ · 2494 "the Spesifikation D. Ens sound ford invaded" equivalent) and subjects it to the CfB-yusl-Opker-Seat "The results obtained are in Table X suaaujaoug" and compared with those of an experiment which was only carried out in the BesiaöT (Baslsöl A).

Table I.

Example ifr. Sestillate
hydrocarbon
fabric oil i «more persistent
Prayer, ^ Fuel coker test
135/223 _fl 9 / 273.9 ° C SSriSni 1
• Basia oil A
iiaoisiJl A 0.0012 Δ? ma Kr 3
2 '63 .5 _BC
(110 öin)
2.03

0098 52/17 85

Even in the table, it is worth noting that Baaia oil A is not corresponds to the stability »conditions for a 3-Mach-Flue * eug, as explained above, while all of the invention Deetillate fuel, which has a low Henge dea phoaphorhaltl £ on seters contain, are well met

Warden In another Verauohaaerie arfindun ^ & AGAA Ba Destillatkrüftstoffe prepared by aan in the Beeiettl smaller liengen a phoapborhaltigen ester dissolves in the same reiee * _f wle in Beiaplel 1 described 1st, north prepared. In the case of dleaer execution afora the Bater is not separated from the all solvents used lubricating oil, but instead the base oil is a bed-like slope of this light sonic oil which not only contains phoophore but also niohtuogeaatstea Auaanggao material and formed by-products. The Zueaaaanaetsung diaaaa Zueata-βtoffee einochllefilleh follows a small thing of a phenol marriage Antlozydationaaittela 1st r / ie ι

fhoaphor-containing JSater 53 Sew.

Triphenylphosphate 3

4.4 ^{t of} methylene-bia (2,6-ditertiary butylphenol) '2.3

Phenol 4.4

Light air conditioning oil Re et ent eil bia 100

009852/178 5

- 15 -

This additive is subsequently abbreviated as "P-.Cotor / 3ohiaierul) coneentrat ⁿ " The results obtained in this process using various types of gel for the CiH-Puel-Coker-Fest are shown below in Table II. The aoiools AD come from Spanked refineries and elnd also recovered in different ways.

Table II '

example
Kr « Deetillate
kohlonwasae r-
BtOffOil B-Xat «r / lubricating oil ^
! Consentrate « i> Puel-oolcei; ..T..t BaelsUl A ^ P mra lie Bohr »
berjertaag 3 » 0.0025 63.5 ■
(109 ain) 3 4th 0.0012 2.79 1 0.0006 3.05 2 6th Baaia oil B
H 0 ₍ 0050 7.11 2 -. Baäia oil C (64 A)
4.83 4 ·
2 7th H 0.0050 63.5
(77 ain) 4th 8th Basic style D
* 0.0050 5.33 2 J3 * 5
(129 ain)
4.83 3
2

O09S52 / 17.85

While Baaiaöl A alone is not the Anforderunßen for a 3: speaks iach-Flu £ »eug ent," rfindundtmcegemäße fuels meet these requirements without 3chwi4rlßkelten · Outside the increased a Zusatg Ainet ^one low <* close the ettorhaltlgen Sonmierölkonientrates the stability of each of the three. others. .Baeieöle 1), O umi J), so that these fuels also meet the stability requirements of a ^ -tfaoh -flsugaeuge.

P Vorsugewelse to the bestiiamten for very eohnelle Aircraft De et iHatkraft not be lcorroeiY materials to copper and silver, and therefore it is UbIiCh ₉ submit such a fuel of the ASTM D-I30-Kupferstreifenkorroeionateet au. In this "test, the fuel is SWEi lanc hours at a Taaperatur of 100 ⁰ C with a polished copper strip in contact brought" The provision Dj £ nc.HD · 2494 requires a Bewertun ^ sslffer of at most 1 at dieaea feet (BewertuncBSiffern τοη 1- 4 and possible). It provides erfindunengenäfie distillate fuels by Zueatβ smaller portions of the P-üeter / SchnieröikonBentretee described above tu a Baeieöl P forth that the provision D »£ ng.RD * 2494 but not entsprichtt the stability requirements of a 3-HACN Plucseugöe ßenUßt. This inventively so-called de-alcoholic fuel is then tested in the AüTM copper tire corrugator. ,

009852/1785

The results obtained are shown in Table III below put together

OJaDeIIe III P- * iäeter / 3ohidiier-
Oil Council
■■ "■" ■■ ■ - '# ■ -.- ■ 4- example
$ Tr » Deatillate
kohlenv / aaser-
atoff oil 0.0010 Corrosion
appraisal
(ASTÜ D «13O) Basisul P 0.00? 5 1 9 α 0.0050 1 10 It 1 11th M. 1

The table confirms that the satisfactory behavior of the Base oil P in the Korroaioneteat dxircb the addition of a small one Amount of the inventive consent rate Aue pboephorhaltigem Seter and lubricating oil are not injured *

Srfindungagemäße Distillate fuels will continue to la Silberetreifenko ^ roeionstest goprüft, "releber aäxin best ent # that a polished Silberatreifen 16 Sttmden at a temperature of 45 ⁰ C with the relevant Kraftetoff in contact brings added · 5 Bewertungaiaußliclikeiten This Seat Bind, the Bewartungsalffer The unchanged appearance of the strip and the rating score for a completely blackened strip are shown below in Table IV

009 852/17 85

- 18 ~ Table 17

example
Mr, Deetillate charcoal
hydrogen fill P-eter / Sobaler oil
Koneentrat jt> Corroaione
advocacy
Silberetrei
fen Ah BaaiBÖl P M * - 0 12th « 0.0010 0 3.3 Il 0.0025 0 14th N 0.0050 ό

The above table confirms that the favorable rating of the base oil P by adding a small amount of the concentrate from phoephoriialtißom Seter and lubricating oil tightly impaired will.

009852/178 5

Claims (7)

Pat θη ta η s ρ τÜ c h # 1. Iteetillate fuel, especially for river turbine engines, consisting of a hydrocarbon fuel oil deetillate and a smaller ile a β-ether-like reaction product from 1 UoI of a compound R (OH) _x V where R is a hydrocarbon residue with lead eu 30 carbon atoms and x means a whole number over 1 f 0 , 5 -ac fetching a kohlenwaeeeretoffaubetituierten succinic acid with at least 50 Kotalenetoff atoms in carbon tasoeratoffeubetituenten or a _{functional derivative of a black acid and O 9} I - 10 isoles of a phoephorbalti ^ en acid or a functional derivative of the functional acidic acid alfa. 2. distillate fuel according Anepruoh 1 * characterized gekenneeichnet "He ale Basiab'l a Flußkeroein having a boiling range zwiochen 80 and 55O ⁰ G and a Aschegebalt of not more than 0.01 part by weight contains 9i * 3 «Deatillatkraftstoff according to claim 1 or 2, characterized in that it contains the ι phoephorhaltige Reaktionaprodukt in an amount of ₁ O oool ~ 0.05 part by weight 5 NC, 4. Deatillate fuel according to claim 3, characterized in that that he produces the phoophoreous reaction product in a quantity from 0.0001 - 0.025 and in particular from 0.0001 - 0.01 wt. contains. 00 985-2 / 1.765 5. Destillatkraftotoff _t according to claim 1 «4» characterized that it contains a phosphorhaltißes ßeaktionβprodukt with more than 2 in the molecule fhosphoratomen · 6 <distillate fuel according Anepruch 1-5 »ι characterized in that it further comprises a minor proportion of _f Metalldesaktivatora, insbeeondere N N l ¹ -23i8alieylidin * _v 2 *> contains propandlamin, 7. Deetillatkraftetoff according to claim 1-6 »characterized ßckennaoichnet that it further comprises minor amounts of other additives" inebesondere antioxidants _t antifoaming agent includes, antistatic agent, iiittel ge against icing agents ^ s the odor, corrosion inhibitors and / or färbetoffe · 009852 / 17.8-5