DE1618553A1 - Improved process for the production of alcohols by the oxidation of saturated hydrocarbons - Google Patents

Description

INSTITUT PiUIiGAIS DU PSfROIiB KES GAKBURANTS ET

1 et At Avenue de Bois Ereau, 92 - RUEIIx-HALMAISOIf, Franlcreieh

Improved process ear manufacture τοπ alcohols by Oxidation of saturated hydrocarbons

It is well known that the oxidation of saturated »linear or cyclic hydrocarbons in the fltiseigor phase in the presence of boric acid (e.g., orthoboric acid, metaboric or tetraboric acid), of boric anhydride or a boric acid • steroid or a ÄajulYalonten boron compound gives boric acid ester ▼ on alcohol, dl · entopping the Xohle & vaaaaratoffen.

The oxygen is gowöhnlloh in a concentration τοη 1 to 25> έ in a mixture with an inert (test such as nitrogen, eye wende t

ÖÖS9S2 / H

uutör

Be =

e>

conditions a Gyelohoxylborat. Other oxidizable carbons · », waeeer ot openly include those that contain 5 bio 8 carbon at one per molecule, such as eB hexane , heptane, ootane, leooctane, cyeloheptane, cycloootane, methyleyclohexane and o-, m-», p-. Dime thy Icy dohexane.

They oxidation temperature is usually from 100 to 220 ⁰ C, preferably swiachen 140 and 190 ⁰ C, the pressure is chosen so that it is sufficient to maintain a liquid phase, and is, for example zwiaohen 1 and 40 at.

The present invention relates to a process of this type in which the boric acid can be subjected to crystallization either directly in the solid state or in aqueous solution by hydrolysis of the reaction products before or after the separation of a rope or the total amount of unconverted carbon and an organic phase is obtained which contains the alcohol sought with the same number of carbon atoms as the oxidized hydrocarbon, which is generally accompanied by a smaller amount of the corresponding ketones.

As ffydroiyaeagans one uses js.B. Vasser or the mother liquors from boric acid crystallization · You 'used the amount of water

~ "~ - - - SAD ORIGINAL

00 * 152/2111

£ at aAsäestena equal to dp? atoOMonetrisohen amount of lyeersaletlen; aan uses in the aiigenelWon Q "1 Mi2 Tolunen-S © £ 1® of the watery! hare to 1 Yolaaen-fcil do * liquid 4b9t £ s" 3 äer CfcySatlojneoa "and works mostly ao" ad

Only canoeing can be reoyoMeiert.

BIe fest® surliokigevGimene Ortlicbore & ur * k «ca Ir eii & ea Ox ^ £ atl <menrerfeJiren wied @ n «rvead« st become »Torstigeweiee n & @ h der Bet ^ drctatioa »so · that they aladeeteas partially

Eat Fos »(ΰ £» ββ Biederen Bore & urelqrdratB is β

present "Terffahren leads to increased yields of Aiko" Xetons.

Creation also applies to verseliieeen Terbeeeeron * gen t- * i Sea terfahren specified above, dl «treant or in

·"* are·

You EsfiMmsg is based on the following

BIe feete sor8efce «evonnene Borslore iBurn again at the datlon des Xolu.einfa8aeratoffefTorsiigeweiae after the / ttOÄ, Y <ttweadet imrdea

iAD ORIGINAL ^ - "

001152 / 21St

acid contains organic impurities, the presence of which is responsible for several disadvantages, in particular the following:

The boric acid is colored and this color is transferred to the alcohol ^{obtained in the oxidation medium.}

When this acid is dehydrated, it will turn brown again observed, which reinforces the above Haohteil.

The degraded organic material _9, the old to the boric acid are reoyclisiert, heuaen the Cbqrdationsreaktioa; They also lead to a breakdown of the reactor.

You erfindungsgemä8e Terbesserung resolves these disadvantages min ^-1 deatens part.

According to the invention, the crude is separated from the mother liquors Boric acid washed either. -

a) old an aliphatic saturated alcohol or an Ieton, the bsw. the 1 to 4 carbon atom contains «at a temperature of 0 to 100 ⁰ C or

b) with water at a temperature "wipe 50 and 95 ⁰ C, while ■ releases to them in water in case letsterem 0.5 to 10 dry 0EW" -9t the washing subjected raw Säiu? e ·.

BAD ORIQiNAL

009852/2151

for carrying out a) the method are preferred Alcohols and ketones those which can be easily separated from water by distillation; it becomes the solvents preferred that at a lower temperature than Vasaer distill »either in a sufficiently pure state or in az-tropic form. Examples of solvents that may be mentioned are Methanol, ethanol, xsopropanol, tert-butanol, acetone »methyl ethyl ketone. The best readings are obtained with methanol.

Preferably, such organiaohe solvent is used, but you can also use a solvent to ^itt: 100ji its weights contains water, for example a mixture Vasser-Hethanol.

The temperature during Väschen with the organic solvent is advantageously between 0 and 100 ° 0, preferably zwisohen 10 and 50 ⁰ O. Preferably, the organic solvent used is in an amount of 0.1 to 2 kg / kg of boric acid, calculated as Orthoboreäure.

It is preferred to maintain a certain amount of free water on the boric acid, which with the invention Solvent is washed. The ones wetting the boric acid cake Mother liquors can be suitable.

009-aS2 / 2iti

The amount of free water can range between 0.01 and 0.5 kg Vaeeer per kg acid, calculated «le Qrthobozäure ·

It is then washed, preferably with VaOaer, which serves to remove the remaining solvent, for example with 0.1 to 2 kg of water per kg of boric acid, calculated as orthoboric acid. The temperature is advantageously "wipe 0 and 1QO ⁰ C ₁ is preferably 10 to 50 ⁰ C.

Any known device can be used in practicing the invention use for the intimate mixture of Ilüsaig-Fest, like E.g. a Snetmoschino, a moving container and analog Devices in conjunction with one or preferably two continuous dry chleudcaj which are arranged in stages, and allow vaschen in the counterstroa.

The organic detergent and the diluted Vaach water

.in Miss & <

can drain separately or I ram the exit of the gate direction present to be subjected to distillation together tu which allows the recovery of the solvent at the top and the wash water at the bottom, which is discarded or * an- * is finally dealt with in order to obtain the constituents surüok- £ ig from it. E.g. this water can undergo crystallization be subjected in order to separate the boric acid therefrom ·.

009852/2151

The following example 1 explains the execution guide of the invention »whereby the« example 14 «le fergleioli serves ·

GeaäS the AusfUhrüngsf or "b) the Srflndung wlleeht Ben crude boric acid τοη the Mutterloagen warde separated" nit w "ter _t Deesen fesperatur switches * 50 and 95 ° 0 'TOrsugsweise" wipe 55 ttnd 70 ° 0 is "ladeei bsb ia Yerlawf des »see 0.5 to 10 Oew.-ji the raw» Jm «ftseaendea Sttare lttst *

You best JEsfebnls ** will «teltef» weea die

of boric acid in the Btfini dee Xamtibmm aeteAel ·. »^,« nd wtle · sviscAen O ttnd 4O ⁰ O l £ sft ₉ web «i this« tlirlJLch aneohlieBend can increase ·

In this way an acid is obtained which is necessary for the Oaqrdation the charcoal barrel toXfe can be served without dad The two Klassisohea Terf honor the factual parts appear. ■ -

This operation remain Xn de "KEAE as the Seaperatnr vas & iv ** sere and the corresponding Terloste" n acid Id Yerlaufe in the above gesetsten Grsnsen "are the amount of water used and the SuntsJctierseit swisohen the water and to washing S & not ure a CUSTOMIZED CATSLETS · You send 1 »out of 10 to 200 animals

'The water possessed. solid acid, absorbed on the dry

BADORfGlNAL QOSiS 2/2111

# _t

Condition, the expiration date etaaMt, and mn leave it Iontaktiereeit depart vary, that no «u» tarke (* u echva ohe) Dissolution of the "sc Sanr" "rf" Igt ·

Mas can eeX each or several HeJLe duroMtüiren, whereby BAn well-known Hiechunge- and / or TronnungeTorrichtmigen used for liquids and petroleum, such as. an Ehotmaecbine, ei ^ TracAin-scA ^ e ^ tffrefraZentrifuge etc.

Criat »lliflierte _P aech of the invented Terfehren evacuated fioreiaures can be eetroocated and dehydrated according to tinea kl *« Bi »chea T * rfohren,« · Β. 1λ a turquoise door direction la fluidized bed or in a rotary oven.

A dinner party »the one preferred luführungßfoxm the invention dare te Ht, consists of »the wttearlge phase, Contains boric acid, filter before irrigation; The Boreäurelcriatall · «earth aneonXi« S «nd geaäS dea according to the invention ? «Rfanr« n

Fltaal of these suetaliohen terbeeeerctng the filter openings are below 2QQ microns and have cB diwmeionen svlecnen 10 and 30 microns "eo dafi ei" al · jeetetoffe, their diameter

ORIGINAL BATHROOM

above this vert · is ι

Examples 2 to 4 explain the "broad scope" b) the invention, but without limiting it! the example 2 A is used for comparison, but not in the orbits of the present invention to be heard.

From this it can be seen that the crude boric acid after Ancestors a) or b) can clean. Both companies drove eu very good results

Nevertheless, nan prevents the quarrel Yörf & hren, that the Yortell opposite the'erste offers that one does not

R 9

a foreign WechflÜBelgkoit must fall back, as in the case of an alcohol or a stone "

Another embodiment of the invention is based on the fact that it has surprisingly been found that there is a critical temperature rise rate which is at 20O ⁰ C and which is the course of drying and dehydration of the recovered boric acid must not be exceeded not followed, one observes not only a aohlechtts functioning Ervärjaunga · - and Dehydratatloneapparatus "special before all · a decrease in the quality and H ^ t yield of ven by oxidation of the Kohlenwaeseratoffs in the presence of boric acid, which auvor

BADORJGiMAL

009852/2151

- ίο -

also dried and dehydrated is obtained Alcohols were also found to be the best brine obtained when under the same conditions ι the drying and dehydration of the boretture at a temperature between 120 and 180 ° 0 were carried out »

The gate direction in which xsan dries and dehydrates the boric acid can be of the classic type, for example a plied-bed dryer or a rotary oven. Zn this type device is a solid (the ¥ öm the crystallization of the mother liquors derived Borsäu ^ t) with a Qua wanwn placed (generally luit or a combustion gas) in Eontakt.

It is essential aar achieve dee MpTftmuaw the "proper gate members erfindunge that the gate of the boric acid is subjected frodümng described under the conditions defined above a Beinlgtmgsbehandlung dee Sype a) or b) above, · so that it is less than 0.09 less woä vorsugaweiee than 0.05 flknr.-J (contains organic products.

A cleaning procedure that completes the previous ones can consists in performing an omcrystallization of the boric acids, taking from an aqueous solution of this compound goes out.

ORIGINAL

009852/2151

1818553

eias? Stock up! »gdHilixsHagefosk know you boric acid in feetea Siietand in one of« inem @ & setros c $ a® β ·! » gaiwMi; sshtf & former water content »nitrogen or I * a £ t flows through the furnace

It is actually beneficial-, i ^ ft instead

als ^ h ^ ratielertuigeoeeiis su Terv? eni.a * c. In the same way on the Yensar "isnipaiäg der L ^ ssäisre ^ uxc.b the Tertra ~ like Sohleziatof ^ -e Seiwef · 1- BurliSt"! «Sir · · die eich

wmm »look like lesissc® luit, esndtra

Bdi ^ ismtieievung d®jr hats »daseh ela« s w $ £ & em luf tstroa

des Torteile deJ ei © skj e & ee? feSmt @egeasftts au S ^ i ¥ «s ^^ üPtsi ₉ Se® äai? im

will, wofcsi iss ferle ^ f'f »this · fe ^ ahrens

der Bf ^^ i ^^^ e ^ Ilgel biMet · die feei de?

this Säxtm

£ ie Sswti & iöÄög ^ etiioä® & $ m & w & @ & ö @ gä is

Method lses% ®ht dsri & t es in isaais factea SäBtekt

ata eia SeB9exs.tiy »iieerllt ₉ s * B.

00fiil / fiS1

a thermocouple in which Sasstroa enters the furnace at « or within it, due to «in electrical or electronic relay regulates a slide that .an Beginning of the Bxwäriningseystaae In dee Saapf attached 1st ι if If the temperature rises too high, the slide is asleep and vice versa. ■

Advantageously, he puts a filter in the gmcstron gate of the oven. "· -

! Similarly, you can _f be the oasis sa output of the oven "because Torriohtungen4tro * ate ea allow the fine particles sitgerissenen su gewiaaen of boric acid, jb.B. through a Cyklon and / or Waeaer Waecfctlnhtlt or through a Boetttartterlaageg d £ «e« · Vase · »kaaa aPaohlleBend dasu serve, the boretture crystal« !! «, di · foa Ä« sr

stage originate, «u wash. '.

Example 5 explains the improvement that occurs in the process, but without it.

It was established that the person was subject to defeydratation Boric acid surslelung the best results bssuglion of, Boric acid dehydration less than 0.09 »

BAD ORIGINS

0H9862 / -21.61

16t8553

Contain less than 0.05% by weight of organic Srodnictea Bufi, i.e. less than 900 each and Yorsugsveis «less than 500 ppm ·.

Ee was found and there let the subject of a brroxsugten Auefühningsiorffi, the fivad of the organizational text cleanings not iu small, i.e. below 20 @ew «« ppei eein allowed. ',

In other words van tmxeivxwft geatäfi one iMTorsugten Execution form a Boreäuro der Sehydratatiolt »the .20 bis

900 and preferably 50 to 500 ββν · ~ ρρη of the organic products removed.

Prevents dehydration "an dl · acid" at a temperature below ⁰

Example 5 explains gleioberee | «n ale The improvement in example 5B is used for Texgl «i« li>. .

example 1

Hau treats the reactor effluent from the partial ·! » OxTdation of the Cyclohexanes with a low oxygen content, nitrogenous acid, in the presence of iron Ifetaboric acid.

BADOR ₁ Q ₁ NAU 009862/2181

This abetroate contains 4.5% boric acid from the formula free acid and oyolohexaaölboraättreeeter ·.

Man. brings this Abetroa at the temperature το »155 ⁰ C, the Exietallisatlanemlaubern the boric acid 1ä So & takt come from earlier operations (they were turned around 20 times) and the old boric acid was saturated ^{at the sea temperature of 50 0 O.}

These mother liquors * ntüMlt «ni0: w« B ^ ttivaleii1 & rgai ^ * cb · acids per leg and 5 g w »rschitd« a · osvuiieoh · Yermtgeliilguwgen, per kg. . - ■ ■ "-. ·" "Man Applies to the Tolua part of the Matterlaugea 4 aeile the organic buum

During the Terlaasen der ^ jdroljstsatk · Al · Miaobaag is brewed to a tea temperature τοη 120 ⁰ C and decanted.

wäeerige- Vham * JUt in wevemtlichan a · what «rige ▼ on Boraaur ·» dl · aan can be auakriatallized by cooling down to 50 ⁰ ouat / or by Eonsentratloa (Abdaapfen dee reverberchüeiigen Vaaser ·).

SAD

Ö09852 / 2151

Β®ΐ <3ΐατβ becomes anafifelie & end yon der wäasii ^ en fnaee through seeded «8i · Hatteslatigen vexden in di ·

The crude boric acid, di · © twa O ₉ -Sä * i <3 * s per kg end Efva 0.15 8 * r _o <~ fl £ orgänieehe festsnreinigiaages "ßthäit. is used for the hydratiinierurag {La 9ln <m Ο.Τβη, daait ei® ernaut% «i« laer oxidation

JkIs X ^ üviifjBBiittel v «» r «ad9t aan Metliaaol in ctsiex- Ifeiige ron

on 1ΘΘ '

& ®m MmmahQu is Si® Bessfl & x® veifi mfeä aehs rtiai ei ·

less ice @ _S O1 Öev, - ^ asder «r organic Mn wlletin & igee Waaeiien ait S3 @« ν ·

aiif 1 @ 0 §9W .- & 9ll «& Box8ätt £ O« rlavibt di · See Kethansie ana den £? Is * lall # ne the

e ££ follow TozEiigeiieise, w @ nn you too

Mclbt di · Bastiäiir © white. Μ · β · boron « acid «Si · bei * ines · ηβ« · η Qsy & aftion des

0098S2 / -2151

is applied, dl gives the same result as a pure

pihlbierune.
Boric acid and does not induce oxygenation or inhibition reaction.

Example IA

Example 1 is repeated by ma dm "washing old methanol ersetst by a Vaechen with water" 4as is verwandet under the same conditions at 25 ⁰ C. The · «» washing also follows • in the final washing with water as in Example 1.

Scots of double washing · If the boric acid is still yellow. Si contains 0.08UmettliqulTalsnt ^ gaal8ehe) s acids per kg and 0.1 Weight of other organic

During hydration, "I Al · BorsJtur" turns brown · Μ · β · Boric acid, which is used again in the oxidation of Oyclehexane

lähXbiflmvs
is "causes a significant ^ / of the oxidation, 9% ά achnellee desqumutsen of the keactor and causes a clear clouding of the organic effluent"

Example 2 . ·

The reactor effluent from the oxidation of cyclohexanes is treated, inöee & «r carbon hydrogen with a mixture of SMieretoffarsen Oxygen ^ nitrogen has been brought into contact 1st »In the presence of ketahoric acid ·

BATH ORIGINAL

009tS2 / 21S1

1878553

San brings this waste stream at a temperature of 135 ⁰ O bit into contact with the KrletalUeationsamtter obtained boric acid which originate from earlier operations (sealing see about 10 MsI have been used) and which ^{were saturated with boric acid at a sea temperature of 48 0} O. One applies to one foluasnteiX of the mother liquors 4 parts by volume of the organic base an

When leaving the Ifydrolysesone the MisohuBg on "is brought to the temperature of 120 ⁰ C and decanted ·

The watery Phaae becomes an essential part of one Solution formed by boric acid; aan runs this · Sbaa «4uroh« in

run filter whose openings a Druchaeseer of 50 Mi-Jcron have · Crystallize aaechlieiend di · boric acid by cooling this filtered Ί # βηο & aaf ⁰

The boric acid is then wiped out by the aqueous hare Separated by centrifugation. The mother liquors are reoyeiielert in the B ^ rdroljreevorriehtung · You get a robe Bor * acid * which contains 0.20 öew.-ji organic impurities ··

The Borsäurekuchen whose Stanperatur is then 47 ⁰ O "is subsequently washed with tfasser at 60 ⁰ O, whereby its Meng 30 OEW · * * ^ corresponds to the Borsäurekuohens, (besogen to the dry state) ·

009852/2161

Kentaktiesseit let dl "same as a" ek 4mi Vfcaeoen, mm wesden 1.2 G "w. ~ £ des see BosoJfas · ins dft * Wsjiotawaeeer g · - give. The washed acid is white, very pure and no longer contains 0.05 Öew.-St organ 1 »oh» Yesiansel deletions »

tfenn with the other same conditions, the sigenieapesa- »door of the industrialized Säuxe 67 ⁰ C ietrcgeft hm, t, eral & lt awn a sttuse of the same EAiohnit, jedooli b * te * gt of the V

1 _t 4 Oev «^ ₍ drawn on the sone i

Examples 3 and 4

Han repeated Example 2 _S mn while the Xeage.de "his Xevpes & tus and KcftfeeJcttesstlt (hence the amount of geluvten Sftuse) nrilirt ;. SI · fi ^ g «tn £ MNi are in the following table

Example Vaesesteaopesatus Baases- Bor- Osganiache

in ⁰ O iMnagß ing »« Buseres- 7 * runr * Jjoi-

ln * t In ^ gongen in>

3 70 - · 100 9 0.03 4 ^; ' 55 50 2.6 0.04 BATH OHiGINAt,

00985272161

1518553

Beiaplel 2A

repeated Beieplel 2 4MeB ma »die SKure ait Yaeeer

30 0 wäechtt said amount Gw. 30-Ji corresponding to the raw treated (besogen au £ _r d # n dry Saßtand) ·

last in the Terlaiife des Vasehene 1,2j6 of boric acid and the latter iXt after the Behan & liäog still 0.15 CSew .- ^ organic ^ ter-

Bslepiel eeigt the importance of Satsäshlieh remains the purity dee erhaXteneii Products »Ungen% @ M _t oiwohl the tie when tfanchen lost Säisreaenge same let Xl ^ In Example 2. But the glelohseitife Iterchführuag & BsiiQgunsen. (V ^ enin-teaperatur «ad Srosenteats of the

it"

the Boreäitr® jtc, ereielea, «as one only Traveled Terlisst on this Säare results.

«Ima? ^ ojitisuierüch «rbeiteiiAeii Biafealt« is staring at whom.

ait 4 fo & mmHß S *>'5ruti> ff at a Seaperftt ^ E- of € 1 O bie

009852 / 21S1

170 ⁰ C in the presence of τοπ Het & boric acid la ubersolmse over the stöcMoaeirieche amount ·

The crude Qxydationsprodukt dft, "looks uagesetstee Qyelohexan and elnenBore & acid esters Tön cyclohexanol contains is at 130 ⁰ O hydrolyzed" Hach gets the decanting aan 2 Ihmsenselno

organic phase containing cyolohezonol and an aqueous, Containing orthoboric acid · Sfcase · The orthoboric acid is made from separated from the aqueous solution by irlatalysis.

'- r ^
The crude Oxthoboreuure thus obtained is washed several quays with methanol and then old water. At this stage the crystals contain no more than 0 "007 oew ·" ^ of organic compounds, that is 70 ppm ·

This Orlaioborsättre is dried in a Botatloneoien, in which the entrance temperature is the ΊλΧ% 1? 0 ^or 0, the exit of the furnace does not look at the Hetaborsttore. After the chain of operations has stabilized, the total yield of cyclohexanol plus cyolohexane τοη 91J (old a degree of conversion of

009852/2161

Example 54. -

This example serves sura? Ergl6ie £ i "g" a1hNi about aie & t ia the ftwhmen of the foolish Srfindu & ff · One repeats da « ia. Example 5- apöhri © teeSa ~ continuJ, © rJLlöM®? Experienced working conditions and the nature of the ssa oagrdierendtn Qjarge remain the same. However, the aa ice drift dee SseoksiBgpafen · introduced air is brought to 220 ⁰ Q »

One quickly observes the acid sticking to the walls of the mustard; In addition, the molar amounts of cyelohexanol and cyclohexanone and the degree of treatment fall to 86 baw in each case. 1öji _t even \ tann aian finely grinds the acid that is preserved in this way.

Example 5 B

Example 5 is repeated, that is, the reaction of the cyclohexane is carried out under the same conditions. During operations, the same old, single interfering condition remains, so that the crude boric acid separated by crystallization is purified even more, eo that this SMx * before the dehjrdratatloa at 170 ⁰ O does not contain less than 10 Οβν · -ρρα terun purifications ·

The purified and dehydrated acid is reintroduced into the Qxy & ationaresJctor .. Venn eioh the chain of operations

BATH ORIGINAL

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stabilized && t »e £ & £ lt aan ice« üoIät * laebettt · an hezanol * Cy © lt * bsximüi £ from 89 _V 6 £ rad eise »reu 11.5 £.

How ready © bem specified * teiai each t®a? Improvements 1 & Terbiis & s & ts alt sindewtesc eifttwp ejsSetEOi

this terbessexemgen applied vexdes · Sgaeami x * 8sltier # a

increased pie parts g @ g # n {£ l) ei? the one with the viewed »isolated applied terb »es & raag received.

Si® bo erlialteaen Terbeasenusgea in

their relative value. less than that, depending on the situation

man a gruSera Saol these terbeeaenuzi ^ en ait each other ned.

Example 6

repeati; Seieplel 1, d * h. Mn treats the oil flow a ·. Hsti ^ äeir & lapeBtan ^^ fdatioxiaxeaictbre alt one of oxygen mxmsä Saserststf * Stieketof ta ^ ucbxss ^ In Aa-essence τοη

Me conditions in the oxidation of this · «Metnjlojelopentans $ with the% drolje» of the product and in the J & ietallismtion of the boron «4iare _t aviegenend tone of the resulting w & pniesn bwee

BATH ORIGINAL

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1618555

Feelings of the union of this boric acid "are generally" alike In example 1. '

"Ta" s & glt eiae weift "Bersliire /, die veaieev" la O ₉ OSI

"Nthüt oafi the ImI 4er Temndoag

OatyflÄtionareektlim τοη
Ec ^ ebaieue vie elae seise BoreÄur * results.

and 8

Example 2, Inde «aw & jevells dse Cteyflation» - t ü-Eexsui tmd Oycloootan behamäelt. Helpers are equal * the Qxyd & ilimaliedingwkgeA this Xoble & Massezeteffe uod

Belianfiluag Cifisbeso & dere the Waechen des BoreÄuremit Vasaer) the same vie la example 2 »

i & d - ^ 'i field examples »obtained © veifle BtssßiUae 0 _Γ 05

ayll * -ii Sabeispielen vtizdes die nolcses insbenteB ic. des Miealrsmg AItöBo3, -Ketoja with Besag * v £ den feettttieten tsieeveltenea

§09852 / 2151

Claims (14)

l. Process for the treatment of saturated hydrocarbons, which contain 5 to 8 carbon atoms per molecule, la the corresponding alcohols and ketones with the same number of τοη Carbon atoms, which consists in dafi. · (A) the hydrocarbons in the liquid phase old a gas, which contains molecular oxygen, are contacted in the presence of a boron compound, (B) the reaction product is then hydrolyzed, (C) the boric acid obtained is separated off, dehydrated and the dehydrated acid is given in the obcydatioiiflEone surüok, and (B) the organic phase obtained is fractionated for separation of the desired alcohol and the desired ketone, ". characterized in that the solid boric acid is dead of dehydration is purified by using them a) with a saturated aliphatic alcohol or a saturated aliphatic ketone with 1 to 4 carbon atoms per molecule at a temperature τοη 0 to 1CX) ⁰ O oier } R5GINAL 009952/2151 b) old Vaaeer contacted at a temperature of 50 to 95 ⁰ C, where a quantity of 0.5 Dia 10 wt. 2. The method according to claim 1, characterized in that d * 0 the Xohlenwaaeeretoff oyolohexane 1st 3 · Terfahren according to Inruoh 1, characterized in that the Borrerblndung BoreäureanhydrKS, a Boreänre or a Boreäureeeter is. 4 · Terfahren according to claim 1, characterized in that dftfi the Caydationa temperature is between 100 and 220 ° 0. 5. The procedure according to claim 1, deduro) hi fctk y ** seI ohiiet \ dafi on the contact with the alcohol or the ketone
Washing with Vaaeer follows. 6 · Terfahren according to claim 1, characterized in that dsü the alcohol is methanol 1st. 009852/2151 7. The method according to claim 1, characterized in that the Vaeeer stated b) a temperature τοη 55 bl 70 ° 0. 8. The method according to Anapruohl, characterized in that washed · boric acid has a · beginning »tea temperature below 50 ⁰ O · washed · 9 · Method according to claim 1, characterized in that it is “el ntmet” dal aan geaäB b) a vase collar τοα 10 bl · 200 0 «w. · ^ aar boric acid, lied to the dry stand, renrendet. Gekennseiohnet 10 · Torfahren according Inspruoh 1 "in DAB oan dl · Boraaure dehydratleiert, including ei · in da ·" for oxidation necessary · Borre Surfagene UANW "ndeln ₉ lnde" a Oa · aan at a temperature "Wiechen 120 and 180 ⁰ O duronleitet · 11 · Terfobren according to claim 10 »characterized, can count» daJ that by indirect contact altVaeaerdeapf under pressure is heated «with the Strook de · Waeaerdanpfee through the (short temperature when entering the SahydratatloneBon is beatiomt. SAD ORIGINAL 0098B2 / 2151 12. The method according to claim 10 »characterized in that the frockengaee leg exit to the dehydratation bone of the Boric acid can be washed with vaeeer »among other things to separate the boric acid particles that have been carried along · 15 · Method according to claim 12 »characterized in that the sum of the washing of the Oasis Tenrendet Vassar is included in the reading of the solid "ans der B ^ rdrolysis dec organic Inas" which from derives from the oxidationesone, the resulting boric acid is stimulated will »to clean the slar · au · 14. The method of claim 1 NaOH "geketmselchnet characterized AAFL _t aan the cleaning of the heaters · continued until 20 to 900 Oew.-files organic irodukte per million Oew.-files acid. 15 »Method according to claim 14» denotes because * the purified boric acid organisohe 50 to 500 Qev * layers Products per Million Oew.-Feile contains acid. BATH ORIGINAL 009βΒ2 / 21Ε 1