DE1518156A1 - Process for the oxidation of hydrocarbons - Google Patents

Description

Hans-Heinrich Willrath Dipl.-Ing. Harry Roever PATENT LAWYERS

Telegram address: WIIAPATENT Postsdieck: Frankfurt / Main 67 (JS Bank: Dresdner Bank AG. Wiesbaden

62 WIESBADEN, ä & n 14. 12. 1965 HildastraSe 18 Telephone (ostai) 3/8730

Gases 1098

lünlytsval Oil Produete Company » 30 »Algonquin Road, B * @ I * lain © s, Illinois - TOA

Process ssutm oxidizing coals *

21 * Basembar 1964 USA patent application /Der.-Ho,-419 810

Bi® invention relates to a process for oxidizing g «- Eohlenwaeseretoff © with formation; of alcohols _r to carry out the OoQrdotion "with simultaneous

dsr form higher Oiydation "produkta ♦ alcohols and! '' © ticularly the Og-f alcohols are in strong ale Ussfange löiungfmittel in mediainiechen and kcsnetischen th, i» the Farföatrieheretellim ^ al "Estyaktione- and when L5" uBgsmittel for substances in Laektsi \ with varnishes as acyclic agents in the manufacture of artificial cleaning agents and all intermediate products in organic safnthea, for example used in the manufacture of plasticizers for synthetic resins.

909807 ^ 10.77

BATHROOM - 2 -

The Öay & atioB saturated hydrocarbon "under Vtrvendung of Luftsausrstoff as Itaydationsinittol has long old one llrthod · -sur production τοπ alcohol""" osw · Ket <m 'iv bclpmat · Dna product d®r Qiydatioiiertnktlon won saturated Kohlmraattffatoffiii contains & lt j "dooh unvtr - / indcfrlicii «ine illsjjhung S @ r product« d «r trsst« »» two «it * n and third Oxy ^ tlkriöatufe, ϋ, Π · alcohols» Al ^; "Thyd © _f ketones" ka ^ oneic acid and s @ rgleloh "n" with ä "i" alcohol heritelluag it is. Naturally, "the oxidation at a Portaohreiten over and above the" rat® stage "should be prevented. eiabriiiet »and i§u-this Zxnok

practically wasa «rfr @ i @ Borstliurt bsEWt, boron oxide used The asiali-forming botnic acid terhi» dert dine O ^ dati ^ n \ mä is cmeohli@Sti?.d under delivery of the gcwUiuiohttn olcohol products and boric acid in aqueous luaung boric acid hydrolyzed ₉ bsw ₀ iaa noroiyd must then be used in practically wnsstrirelt form 'surÜQkTSXwrkndiJb ^ bsror further use as faagnittol

wasssrfreiee boron oxide "is a jedooh feft-ary material $ ao da3 sißh .tin heterogeneous Reaktioneo gemie ^ li gives the Kohlenwaaserstiiffpartsuir. There sol oh «

^ Suggestions urüatäEdlioh are "it is very desirable" a

^ Fangmitt ©! ^ u Terwsndenü the si »homogeneous reaction mixture ο with the »hydrocarbon partner forms» so there is a better one -J contact and © in® wixkeaswrs interception of the alcohol product svslslt will be. The invention requires a new asset,

BATH ORIGINAL,

»Ma? Allqrlatt & bovatf 4a · eiae h © »ogeise (UNt ~ 'KOhltinwipMatofffrartner bildett« a # auitriem XHSt • ± «h Alkylaet & feer & t with bucket continuous

! Dengemäft sees di * Krfisdu "^" V "s £ ahx 'n EIAR g®sättigt # r Kohltmrnattnitoff · Alcohol · tos * bti you Amn geaftttlgttn KohlenwReiieratoff in contact with

Gas unä a * m AHqrlffivtaöe ^ it, under Oxyda- «Rhitst and« iba * Dialkylbcreaur »-;

• tntii T "II dl # s" r "iaHqrlfeoreäur" under picture wüneeliten alcohol "uM boiwäur" hydrolysed, the alcohol "separates. Part of the biaikyl & oreaure with the formation of * lkylmetaboraii umeetsst and the latter with further »saturated carbon dioxide and eaueretofthaltlger. ^ s GeiaäS a beeonderen AuefUhrimgasform of: -]-making CyeloMesylalkohol is hergeeteilt "by" rait to Oyolohexan into contact air "ad Cyelofeexylaetabörat r.uf a Tesqpenttur tone about 140 bie about 18O ⁰ C to form τοη?

"Rhitst, about 45 never about 55 ^a 'of the boric acid ebti ^ imit and with the formation of the desired Oyelocd iMsjlalkohole-mi aqueous boric acid l« rarolyei «rt» flon ^ Cyeloliexylmohol separated each product \ m & the weight ^τ ίοηβ ^: ίια ^Α * from d .α Α * «Al ^ irolyeegssisoh wins _{for the} latter with. * 'The .yv * blelbenden portion τοη Di © yelohe; qrlboreäi * re with one

O O

-j? eaper "tur" Uure iron etwn. 100 at about 250 C with formation ^ - '

of 'oyolohexyl-netaboritt converts, letsittree in practical

.-..- ■. "BAD OKM

Zsiatasd gciwiias * mti with further "al" A

Dar saturated® Kehlemraeswretof f »de» - as Atufeaeeiiaterial

btnmtst w®y $ @ n knan, esrlMilt wrsö | £ sw @ ± $ e about 4 "to about carbon atesad» ^ r kasut _{: 3 be} lieyeliseh or aliphatic, belong to the g®§i.0i@töB saturated carbohydrates

Fentosi »leopentan« ad Ters @ hi «cl« iie Strulcturt-: n _# 3I «pt ^ i _s Octna, Ώοο ^ ιη» Dsdeean »üöetrMeoan, tisiä d« rgleioh @ n · Hierau gthSren aush Oy el open tan _f pentnn, Oyolohexsn, f ^ ethyloyolohozan »Oyöloootan, Oyolododtea» and

Ausniohender Bsmek applied »around the li

flüieig su hold »Xa fisltn cases, Lxtftdruok nutogeae SMök anfflr © ieli®nc! _{f you} see in the course of the .oxydationffeaktion @ B, twiefeelt _e Although the temperature "at the di® Heaktioa" is durohgefUhart, gwiiohess about 100 and '225 ⁰ O or m®hT eehwanktn kasm "-' wiri -vo ^ jsugswele * - the oied point of the

the Meaktieneb ^ conditions niefct exceeded "WiiSloaäSlg you work in the field of clay about 140 to 180 ⁰ C. ®twa Aueh is" e sweekmtttigf account taktdJfitter the ßeaktioiuipartiier on beirenaseji, including prnktlsoh

to mmnlg ^ T as # In @ T ^ llstäsiöig® üawandlimg def Kohlenwaeeer »« toffb§-i®! ii @ kaiig Ji) Dwwnshgsm ^, ιιϊ ^ twktursi · Bd For example

iie l ^ ßkticiispartiiss ¹ irnttf leaktionsb® »

-j diaguiigea wühread ®ia®e ZsitraiMas tsh etvn-1 to about 10 hours in contact brought ssu, wiihrend to a 'low idle .verhältnis- ^"T © mwaadluiig®grad content _s of vorssugaweiae

- BAD OR! G; ^ ä '~

518156

aioht is practicing * «around 30

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from molekül®! ¹ «» Barnim toff in ftraa van '£ ttift ββ «ι?

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909807/1077 bad

Vraktlmt & e & tugm 9 g $ ht »In PvE & tionltvttini will KohlemmeeMWtoftt @bt »abtat-tillitrt umä ira KF «i®lais £ sism 03 ^ 4atl @ n» g $ fii 1 ttber line 10 lind line

2 old feil d #? IiÄltfiwae «tiret @ ££ b # ®eliiek * iiig siS3ett © 3cgel # ifc» t «orsi & ux« wlrA. au · - & @ a Pyaktlonitniu »9

11 "In kbhar @led" Ildl9 F ^ a & ttoii

In G®fä0 12 wlTd'dl « Sag uiivch LeIy- ^ r, g 13

ot.h5 .: ^Vl _i;

al ^

old Wamtr b «ltand * l * _f

and sit dom -g «wütt» eht «n alcohol Aikoholprodtdct -

ii «» leh Ia

ι: ϊϊ

12 flnd @ n. I) Ie «Holds» 15

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wltl »sat« geleta

umi Scr Dla2Jt3rib9f «äarci ... imft 3ox @ & u? E alt i © ff SlallEyXbonBauxit tntMP'BiXAine το »,

BifH # reaction 3.MJt see i »qu» m t} @i

i) «Mieh vob about 100. bl · e% wa; 25O ⁰ O

will

under reduced

909807/1077

^BAD orjg ^

-Print trimmed. and in these days all «oil« la «^ en of raindesttne 50 ° C are rooted * to di® iTa» »tzimg το» boric acid and 3irilkyrboraäur «, with a pmsendon.G-eaehwlhdiglceit au cause« ice · head line 17 serves ζιιτ 'distance de® ">7r' * eera au4 the Troc & ner 16. B? β / lkylmstr borate is rliökgev / onnen through line 5 in KohlenimraeeerBtofflSeuBg and ssusi O ^ dationegeväSiol 1 ale I-'mgsend intel the llcolcolil Education siirüokgösohickt »

The Ikylmetaborat® completed as a catch agent according to the invention are, for practical reasons, a derivative of the respective irolilenwiveseretoffbeeohiclcimg *. At the same time the KolileBwaaerstoffbesoliekung tua dodeorm is ordered, so the Bodecylmetaborat® is used as the Dmetaborylretpborat Oils Binlkylbora'iure *

The "rubbing up of the first time"".. after the invention is given in an overview based on the drawing," but various modifications can be made "without departing from the idea of discovery · !! In sswel separate strUra " : in which one under delivery the desired alcohol" and the boric acid is hydrolyzed "while the other is combined with the hydrolyzed boric acid and reacted

Again, alkyl metaborate as a catcher forms. The -V-uaf uf voa ^!) Xydi'tionai; sffiß k ⁿ nn nlao et ^ tt in iüv / ei separate

• - bad os; £ ::: al,

^l i D 9 8 (J 7/1 O 7 7

Stream, as oe multiple depths are divided, "u will""" as " velvet ""tofractionated" to separate out aiioht converted coal waaeereto.fr "and the higher boiling JSi- &lkylbor" aur # £ rakti "m germ sittilekgewesiiies and in stwti ströme divided fjerdsn »ton which one« under Mefern the desired alcohol »and Bortäur® ftydrolyeisrt,

the cmdtx "with the H ^ drolystbörtäur- * rer" i "igt usd RUokbiiausig dt" Al3eyl? sst & liorats al "? a" gaitt ·! uag «· wi? d ₉ / indar-sraelt» kaxn auoh d «r Auelauf rom Oxydieav vessel in BWdi gttriomt · flows wit» a? vüiuit «trltgt w * r4 * n» B «r« ine electricity can in Chftgtnwart d « e not täii "· ETST * n * carbon awa" stystoff "e Nuter delivery dt« «effüaiioiit * n alcohol" and d "r Bomäur" hydrolydtrt sti ^^ n, vtährmu the andtrt gtrom with Iiydrolyeelsoreäur "v" is reijslgt and sialylboric acid and boric acid under Rüokbilduag de «« earth »

The alcohols produced according to the veriolxren of the invention generally contain slightly Alcohol product in the uemiseh with Wa «@« r «toff βκ contact with an Iördri * ataly« »tor under% drlerBed & Bgtiii $ en treated» never generally known in the eehnlk irfc, example «-» white * the ketone « htm » Aldehyde content of« alcohol products · slightly «ü» alcohol hydrogenates »if you use « a hydrogenation catalyst such as copper »zinc oxide ₉ chromium oxide» manganese oxide, Hiakeloiyd uew.

and also Melmetallkatalyfiatoren »like platinum» palladium or »

9098 0 7/1077 ^{SAD GR:} --a.

their * öa ^ r & e used · Hydrogenated peratures are generally in the i) © relGh of about 25 Ms about 25O ⁰ C. The ratio of hot water to ketone bsw "Aldehyde is usually used as" Partialdruokwn Waseeretöff and can be about 0 " 68 to about 272 at each close to the nature of the "alcohol products", In the alIg @ js "ia # B ftthvt a higher Dmok au one?

Me follow @ üSe »Examples serve for further explanation

Bine Migefcung το "Bodecyl metaborate and Dodeaan h as follows"? Ge * tellti 6.12 g Bcwäurft, 32.8 g Bodeeylalkoiiol mad 100g Bodtean be auemsmengerührt and a Jeiapera "· door r <m 170 to 190 ⁰ C" rhitiit · Bae ReaJctionewaeeer is koatinuierlieh * by it with Dodeean in a head Kondensater au · "Feedb ^ ffimit, wlthreM surtiokg as aiseotrope Misehu & g the surUekgewonnene Dodeoan sur Haaktionsmisohung" derives wid "Haoh Beendifung irmtetssungf AENV the imn away to the mixture in the absence of? / Asaer in the condensate recognizable staoht "is wide Meage B @ de @ at the Heaktieiiaffiiachung that this about 15 Crdw ·" ^ Bodeeylmetaborat and 85 B @ d "ea" contains "

The temperature of the Eeoktionsmisehung is ^{lowered to about 154 0} O, the Hie @ iiu2! G placed in an ossification vessel and diluted with nitrogen · air ale @a «» the about 2.6 % oxygen

909807/1077 B ^AD

Contains, äuroh the reaction projection with a speed Ύ & Ά 0.569 mol per hour living in a® lateral space a of

Θ hours - blown. .

The resulting Reaktiansraiaehiusg »which is called Qxydat OtKSiCl-ITiOt» is practically equal shares in & w @ i & · * ■ »Xagt« borrows tttsgeeetatsa Bödeeais is stilled from the first part aM ^ and the vtetllohe Borateaterfraktion »contains the Bodasylboraaur®? firö adt warm VJasser hydrolyzed · bar "hiiirfeti entistandene 33od" cylalkohol is as upper layers of fltleeigen g®w © na @ n * DI® lower Sohiöht is

Boric acid is combined with the second rope of the oxidate and put in a distilling flask at 100 to 60 ° 0. The ira flask Eüokstani let tine ülSeusg from Bodesyliaetaborat in Boä «0Bja · Bieser lUlokstsosd sueasnaen with ssussätssliöhem Prlaoh» ilodffioan in ßoloh ^ r Mtngt »da0« sine Beaktionsmieohung with about 15 Gw.-fletals -> 85 Bodeofm. educated

in-da "Oa ^ dstiensg®fäi g" g®bentimd with nitrogen Air τοη «inem -oxygen content Tön S» 6 '· - becomes duroh

hixtiur @ ligeblasei! _e Si «final pro« »@ inaöhlieiSli @ fe» tma 13 f? S * 0 ^ ^ »- Κβ ^ οη, is un-

BAD OR'QIMAS '11 -' 909807/1077

A mixture you Cyeloheaqrlmetaborat In Cyolohexan is duroh ZusararaenrUhren of 311 g Boroayd and 100.2 g of cyclohexanol and heating to about 100 to 140 ⁰ C "ubereitei · The Beaktionewasser is continuously au · the mixture recovered in a Kopfkondtneator and the cyclohexanol is in the uefäd Once the reaction has ended, which is indicated by the PehSn from Vfaeetr in the condenser, 5000 g of Cyoloh »xan« are added and the mixture is transferred to an Oaqrdiergefä0.

The temperature of the house is raised to about 165 ⁰ O and air diluted with substance of about 6.5 oxygen is evacuated by the raactionimiaohung with a @eeohwinsligkeit of 231 93 HoraaXliter per hour in the course of 8 hours · The Druok is at 9 » Holds 5 atm · The gas that is withdrawn from the top is cooled to condense water and cycloliexnn »The condensate, which consists of two phases, is passed into a separating vessel» where the cyclohtxnn is separated and the reaction vessel is taken to the office «while the water is being poured off.

Me received Reaktionsiaisohungf the so-called Oxydat is in "w" i praktieöh gleiohe ropes divided ·! Lieht uragesetstes Oyelohexan is distilled off from the first part and the remaining borate esters fraction Bioyclohexylttoraäure wirfi with warm water hydroIyeiert "Dan thereby obtained as a product

Cyclohexanol is used as the top of the non-miscible rails

909807/1077 'bad OEiamM.

- 12 -

obtained "bit lower rail with the aqueous boric acid is cleaned with the second part of the Öagrdate T cleaned and thus obtained in a single distillation flask to 100 toi · 160 ⁰ O. The water is distilled as aztotrope Mieehung isit Öyolohaxan and the latter is obtained and with the Oaqrdat im ! Alembic combined. The Eiloketand remaining in the flask is a solution of Oyolohejylmetftborat in Gyelohexane "He will be mixed with friaohea sue" essential "n Oyclohexan in a large amount" that one can make a lysis with about 15 uew · «^ Gyclohexylmetaborat? Cycloheacan gets added to "OxydiergefäD, and Stieketoff to about 6.5 f 'oxygen TerdilAiie air as beeehrieben above hinduriihgeblasen by this Reafctienemisohung you" End & is usbeute ungeflüir 85 ^ conversion at 15 ¥> ·

«15 - ■

BATH

9098 07/1077

Claims (2)

Patent a naprüahe 1 · YerfaJir «n aar conversion of iron saturated hydrocarbons ia alcohols, as a result of which one forms saturated X © lil # Mwa« s # rst © ff on contact with an oxygen-containing alcoholic acid alksrlaietaborate under oxidation conditions srhialstyl and a "a bargain of Malkylfeöraäi5r" separates lister formation of gewtinaeliten alkohola and boron "eäare hydrolyeiert, AEEN alcohol and the product you gewisntf Borallure with another rope Bialkylbor-" acid iintf ^ formation of Aliqrlmetaborat and the latter sfättigten with g ^ hydrocarbon and oxygen 2. ¥ erfalire »after Aneprueh 1» characterized in that »that animal saturated« hydrocarbon on contact with Ä @ m oxygen-containing Sas and the alkyl metaborate to a temperature in the BSirsieli tor 100 to 225 ⁰ O is obtained. 5 · Procedure according to claim 2, characterized by the use of a f «Mp« i? Atttr from 140 to 180 ⁰ ₆ β Terfaunm ßaeh one of claims 1 to 3, characterized by the fact that air contains oxygen-containing gas. ash. One of the speeches 1 to 5 _f marked the use of I ₁ Uf 1 ^ _{AL diluted with nitrogen} β «method according to one of claims 1 to 5» It is well known that the alkylic acid of the alkyl acetaborate originates from the saturated hydrocarbon. »Is about 45 * 7 A method according to any one of claims 1 to 6» daduroh gekemis "leimst that ά @ τ Malkylbors & ureanteil» which the Hydrolys "is lanterzogen to 55 i" of Blalkylborsäure formed in the Oxydationareaktion " 8 "Terfataesi according to one of claims 1 to 7" daduroh characterized in that the ratio of saturated hydrocarbon t oxygen-containing (Jas and alkyl metaborate and the reaction time of the oxidation are regulated so "that the conversion of the saturated hydrocarbon does not exceed about 30 $ ^ e Buröhgang" 9 · Veiefahren is broken for a ά @ τ claim 1 to 8, "gekennzeielmet by tHe the Eeaktlonsmlsohung in ewei units" whose erstepsur distance not uxngesetzten Kohlenwasserstoff® "ron the Biylkylborsäure prior to I |? Sr £ distilled dlys9 and the second portion with the boric acid formed in the HydroIyas at a temperature in the Bersleit ron 100 to 250 ⁰ O ssweoks le effect of the reaction zrtlBQhmi Bosäure und Blalkylboreäure is treated * _e " _: · ■■■. ' § "'" ■ "" ■ "■" ■■ "■ ■■" ■ "" ■ "- cc 10 »T®rfahren according to claim 9 * characterized by» that di «ο siwlsohen boric acid and diaDryiborßäurs under ab- » of the water mza of the Keaktioftsmlsohung: durehg * leads. 11, method according to one of the speeches 1 to 1O ₉ in that the saturated hydrocarbon contains 4 to 20 carbon atoms 12 «Procedure according to one of the tests 1 to 10, excluded duroli the use of do de can and extraction of dodeeanol as a process product * 13 · Procedure according to one of the claims 1 to 10 through the use of cyolohexane and the extraction of Oyolohesanol ale process product 0 9 8 0 7/1077