DE1645734A1 - Process for the production of solvent oils with a high aromatic content - Google Patents

Description

Dr. Karl Th. Hege 2OOO Hamburg on August 30, 1957

Patent attorney Srosse Berostr. 223

Telephone 39 62 95
Telegram address: Dölfnerpate | D 4 0 / d T

Standard Jociete Heine folder: H 1205

Francaise

B e 3 dir ei

23.30 ΰίΕΛΙΏΑΗΪ) oOCIETE ΑϊίΟΗϊΚΕ FEAFCAI3E, 5, AvonuG G-ambetta, Oourbevoie (oeino), France

Process for the production of solvent oils of pale aroma

Addition. Door patent grant E 25 5 ^ from December 14, 1964

housing iiiiriiel'-auig viird the priority of 6 September 1966 .QX 'fx ^ anzüfjxüchen PatentanniGldung Ho. 75 4-44 in claim

, vonommeii.

Mc Egg-rin

E-i-.rinavj.ij L-jmeets oin Loriun ^ smifcbelol and a 7-

k ^ onuuoiio. dos Patonts .... (Patent application E 2ü $ 44 I7d / 2pb) "

l: .u oiij. / orfahi'on aur Herat ollunr; of oils from high JjOrjua ^ jvormüjon, boi dom 'Jal.ou extraction eiiiüs petroleum duatillate-o.-j i.iij υLiioui:, ol ^ kui / un JjouMn.jijmitt ^ -l a ßaffinate with a /i.'j^oaitübc -Jloiibo-i'ZoiiGüante in Jioroioh from 0.815 to 0.85

owe » ⁴ '*'

009829/1277

and a solvent extract made, the Extract With nioht-extracted egg distillate mixed and the Geaieoh duroh catalytic hydrogenation into an oil of high dissolving power Is transferred

For the term "viscosity-density constant" see Zerbe, "Mineral oils and related products" »1952» Pages 621 and 779 » as well as "ABO du Grab β age", published by the Institut Franoals you petrol «, page 82.

Al · selective solvents can oan all for the Extraction τοη aromatic compounds known Lorning · *! T ~ tel »like furfurol» aniline »sulfur dioxide or phenol, use.

In a modification of the above process, the invention relates to a process for the preparation of solutions of oil-based oils des made from one crude oil at least two oil fractions and an extract containing aromatic hydrocarbons is obtained from at least one of the oil fractions »and which is characterized in that the extract oil is mixed with at least the other oil fraction and the extract oil and the oil fraction (s) are catalytically hydrogenated before or after the mixing

At least three oil fractions can also be produced are extracted from all these oil fractions and before or after the hydrogenation of the rest of the fraction, the rest

- 2 ~ 009829/1277

Mixed tractions

The oil fractions can be distillates, or at least

one of the factions tsim. be a topped Eohöl (i.e. the residue left after the A distillation of the lighter constituent parts) _o

The hydrogenated extract and the hydrogenated oil fraction are the hydrogenated oil action can be reduced to one by distillation or several £ 8sungs2iitt @ l {Sl £? a & tlonen Y to be worked on «

Yorsugsweis «Confess that (! Eiaieoh from extracts! And oil fraction (s) en 30 to SO Gew, - $ from Estraktul and au 70 to 20 Gewe- ^ from the dlfraktiono

The invention also includes those produced by this method LSsungssittelule «

The erfindimgsgemäs © huTgo-ymllr ^ n Lössingssiittslöla Ιεΰηηβη

TiskoeitSten tob S ₃ 5 M © 4-50 0St ₉ hesiiwt at §0 ° C, have «

The arMBatesredefeffi: Iztraktii: -, " cores with the help of the usual solvents such as furfurol" -aniline "sohulfur & loxyd or phenol, are obtained f hsTorsugte X ^ sungenilttel are hienol and furfurol ·

The catalytic Hjdri © rtäng imm au. the usual hydro

like Ozyäesa imä hsm, or sulfides of

Metals »like VaaaiiuB * Ohrom ₉ Itegasi ,, iron, cobalt ^ -liocel» molybdenum »sense, Mc & el-Kol & ßlt-MoIyMtln or Eisen-Eobalt-Molybdenum ₉ durohgeftösrt werä @ n _e the catalyst can sloh on a

009829/1277

such as aluminum oxide, magnesium oxide ₉ silicon dioxide, zirconium oxide or spinel ₉ are found *

Me hydrogenation can be carried out under the following conditions will ^

temperature » ⁰ O 250 to 400

Pressure, bar 20 * 80

Durohsat speed (building parts & * e

oil Raurateil catalyst per hour) 0.3 "& yS

Hydrogen supply flow rate 11 (Eamateile Hg ₉ uisgereobnet auf

H »S.P.» Per portion of oil) 100 "500

In the following examples, the prosentual Shares in aromatic, naphthenic and paraffinic acids Carbon atoms according to the Brakes method by ultrared spectroscopy bestiaiat {see «Brennetoff-Gheiaie, Volume 37» 1956 » Page 263 «Measurement is carried out according to the ASSM test standard D-1500

example 1

A light distillate and a Bztrakt from a distillate with a medium boiling point, both distillates, serve as starting materials obtained from a Tia Juana raw material. The light distillate is the fraction comprising 11 ToI .- # which is between the 41 Jt distillate point and the 52 ^ Thursday still atpiuakt of the crude oil passes.

The distillate of the middle boiling point is that of the distillation of crude oil between 55 and 61.5 ¥ ol · - ^ won traft »

0 0 9829/1277

tion. The extract will be treated from this fraction Mt phenol produced under such conditions that after dea Removal of the phenol by known methods, the Raff inatauebeute 44 # and the extract yield is 56 #.

The other characteristics of the light distillate and the extract can be found in Table I

gave all I.

Shallow characteristics of distillate extract

Density at 15 ° 0 0.908 1.003

Flash point (open cup) » ⁰ G 178 235

Viscosity at 37.8 ° 0, oSt 21.5 838

Viscosity at 98 »9 ° C, ES 3.63 18.76

Acid number 1.8 2.84

Aniline point »° 0 71 24

Pour point » ⁰ O» 45 ~ 6

Aromatic carbon, § @ w _e "$ 20 36.2 Faraffinic carbon" dew .-- ^ t * 51 42 "2 Laphthenic carbon" 8sw "^ 29 .21.6

Bas distillate unö, des? fetealrl we ^ desa S5 «i ® $ m @ wi © © sdsoh from £ De@tii2.at wb & 65 $
ledingimgen hydrogenated ι

(ο Sea temperature, ⁰ C 280 1645734 Print bar 60 BurehBatsgesefewindigkeit 0.8 WaseeretoffsufiSarunga «·
sullen rindness 300

Number of. Steps or

The hydrogenated mixture is distilled, whereby the fraction from 20 to 90 f- transition represents the Liismigeiaittelöl «The results can be found in the table below:

Saitelle II

Gate of the Haoh the
Hydrogenation Do that
distillation color according to ASSH > 6 2.5 Yiekoaltöt at 98 * 9 ° ö, cSt 8.7 7.85 Viscosity at 37 »8 ° ö _e • 138.13 111.50 Viscosity index -25 -15 Acid number 2 track Dicht® at 15 ° C 0.967 0.964 Blaastpirakt (open
Mug), ⁰ C 233 ■ 216 Sulfur, ßew _e - ^ 3 * 1 0.35 Aitilin point, ° CP 50 51.9 6.5 8.11 117.78 -12 track 0.962 202 0.3f 52

Al® inegeassetoSf © Iisn @ m © in

a 44 # Kienplöder ftarftirolextraict ana of the heavy distillate fraction of the £ 1 & JiIaSa-EoMIs, the light distillate goes in the distillation of the original SIa Juana-Bohuls tone 41 to 52 ΤΓο1 - $ 1Sb% s ₉ which is iaittler © distillate the 16.5 VoIc-5έ uiafaeaende FmktlQH τοη 52 to 68 ".5 Υθ1 ·" -3 & ₉ and the soliwese distillate is the fraction of the crude oil _o

The Affected from d @ zs distillate of medium boiling point is manufactured according to example 1 «

The other characteristic values of the starting materials can be found in Table III «,

009629/1277

Table III

Characteristic value

Density at 15 C Flash point, C Viscosity at 37.8 ° C, oSt Viscosity at 98.9 ° C, cSt

Acid number

Aniline point, ⁰ C Aromatic carbon, wt.

Paraffinic carbon, weight - "

Haphthenic carbon, Gew α-Jt

Light medium heavy Distillate Distillate Distillate

Extract from 44

the alttle extract

ren destil- the heavy

lat

distillate

0.910 0.938 0.950 0.997 1.001 cn 178 240 278 278 Oil 20.27 208.65 - 890.30 not measurable CO
-Γ- 3.53 12.56 36.5 20.06 108.58 1.7 0.9 0.7 2.9 3.2 71 82 Trtoht mess i 20 16.2 17th '32, 6 40 51 49 48 42.2 40 29 34.8 35 21.6 20th

Ss are different mixtures of the starting materials produced and first hydrogenated and then distilled «

Mixture (a): light distillate 30 wt

Extract of the middle distillate 70 % by weight

The mixture (a) is hydrogenated under the following conditions «

Temperature, ⁰ C 320

Pressure, bar 60

Thermoset speed. O ₉ 8

Water feed rate 300 tree parts

(N, TP) per component of the mixture

Number of levels 1

In the subsequent distillation, the fraction passing over from 5 to 97 is obtained as solvent oil.The results can be found in Table IV.

table IY

Characteristic values 8 ° G, cSt Outgoing
gemisoh Do that
Hydrogenation 1 / 2- 945 Solutions bit
telöl after
the destil
lation color according to ASIM 9 ° 0, East > 8 4th , 08 ■ - 2.5- Viscosity at 37, 149.54 106, »39 7th 114 Viscosity at 98, 10.0 8th, 8.85 Yiskosity index 26th 28 track 26th SJtureahl 1.5 0, track Diohte at 15 ° 0 0.972 202 0.942 Jlamnpunkt, ⁰ O 204 57, 216 Aniline point, ⁰ O nioht
To be swept 58.3

Aromatic carbon,

Weight -Jt 32 32 32

The Genisoh (b) is composed as follows *

Light distillate 23 wt .- * 320 Medium distillate 38 wt 60 Extract from the middle distillate 39 wt 0.8 ■ Hydrogenation takes place under the following conditions 300 Temperature, ⁰ C t Pressure, bar Duronsat geo speed Waeeeretofi'suff & riragsgesobwindlgkelt Anoaiil of the steps

- 10 -

009829/1277

The hydrogenated mixture is distilled and the 2 i> transitioning to 92 group represents the solutions! Ttelöl is "The

8 ° 0 _f Table Υ mixture
(D) laugh the
Hydrogenate LSsun old-
telöl after
the destil
lation Characteristic values 9 ⁰ C, 8th A. 2.5 color according to ASfM 156, «3 91.10 112.36 Viscosity at 37, east 9.77 7.62 8.52 Viscosity at 98, east O 21 22nd Yiskoeitfttsindex 2.5 track track Acid number 0.952 0.930 0.943 Diohte at 15 ° C 208 190 210 Flash point, ⁰ C not
measurable 71.2 70 Aniline point, ⁰ C

Aromatic carbon, £

28

27

27

The mixture (c) is composed as follows: Medium distillate 60% by weight ( Extract from the heavy distillate 40% by weight The mixture is hydrogenated under the following conditions:

- 11 -

009829/1277

320 60 0.8 300

Temperature, C

Pressure, bar

Durohsatzgeeoh Speed Hydrogen admission rate

The hydrogenated Genisch is distilled and ttelöl won 10 transitioning to 92 ToI β -4 "fraction as solutions!. You can find the results in Table TZ.

Table TI

Characteristic values

color naoh ASTH TiacOBity at 37.8 ° C, cSt Tiskositat at 98.9 ° 0. cSt Tiskosity index AcidEahl Density at 15 ° C flash point (open cup),

Aniline point, ⁰ C

Aronate high carbon, wt

mixture
(ο) Haoh that
Hydrogenate Looseness string
telSl to
the destil
lation > 8 6 1 / 2- 4th 824.87 467.64 244.07 25.0 19.1 18.3 T 14th 15th 3.7 track track 0.956 0.945 0.948 250 224 256 75 76.8 75

31

30th

30th

The mixture (d) is composed as follows: Middle distillate 30 wt .- ^

Extract from the middle distillate 35 Gewo -? ( Extract from the heavy distillate 35% by weight

- 12 -

009829/1277

The mixture is hydrogenated under the following conditions «

Temperature, pressure, bar

Overhead speed Hydrogen Sniffing Rate

320 60

0.8 300

Bas hydrogenated mixture is distilled and the from 10 to 95 by volume · tf> on continuous traction as solvent-oil to "Results are shown in Table TXI.

Table 711

Characteristic values

Parbe according to ASTM viscosity at 37.8 ° 0, oSt viscosity at 98.9 ° C, oSt viscosity index acid number
Monte at 15 ° 0 flash point

(open cup), c

Aniline point, ⁰ C

Aromatic carbon,

mixture
U) After this
Hydrogenate 1 / 2- 951 Löeungeait-
telöl neon
the destil
lation 8th 6th > 05 4- 1004.56 326, , 55 4th 425.9 27.7 15, 18.16 0 15th track 15th 4th 0,
• track 0.971 186 0.950 238 69 250 not
measurable 69.7

31

30th

31

- 13 - 009829/1277

164573a A'i

The mixture (β) is composed as follows Medium distillate 20 wt.

Extract from the middle distillate 45 wt. Extract from the heavy distillate 35 wt.

This Geaisoh is among those for the mixtures (a) to (d) The conditions given above are hydrogenated and then distilled. In this case, the fraction passing over from 3 to 80% is obtained as a solution of oil. The properties can be found in Table VIII »

Table YIII Solvent oil Characteristic values '. 4th ASIM color 491.7 Viscosity at 37.8 ° C, oSt 17.99 Viscosity at 98.9 ° C, oSt -15 Viscous! Ity index track Acid number 0.951 Density at 15 ° 0 236 Flash point (open cup) » ⁰ C 60 Aniline point, ⁰ C

Aromatic carbon, weight 5t 35 Example 3

Am 56 pounds extract from a distillate of medium boiling point, which τοη that in the distillation of a Tia Juana crude oil 52 to 68.5 vol. - £ transitional fraction is shown under the following conditions hydrogenated ι

009829/1277

4 <

Temperature, ⁹ o

Pressure, bar Durohydrate resistance 0.8

Rate of hydrogenation The hydrogenated extract has the following properties: Table II

Characteristic values

extract After the
Hydrogenate > 8 5.5 890.30 393.16 20.05 14.33 <0 <o 3.7 0.10 0.997 0.975 256 224 not
measurable 48 43 42

Color according to ASSC viscosity at 37.8 ° C ₉ cSt viscosity at 98.9 ° C, oSt viscosity index acid saw! Density at 15 ° 0

Flash point. (open cup), c

Aniline point, ⁰ C

Aromatic carbon, wt .- ^ t

By distilling the hydrogenated extract, two fractions are obtained, namely a fraction (a) from 0 to YoI.-Ji and a fraction (b) from 5 to 97 vol .-? *.

The light and the middle distillate of the example are hydrogenated under the same conditions as the extract of the middle distillate. Then two mixtures with the

- 15 -

009829/1277

the following compositions are made:

Mixture A:

Hydrogenated light distillate Hydrogenated middle distillate fraction (a)

Mixture Bs

Hydrogenated light distillate Hydrogenated middle distillate fraction (b)

Mixtures A and B form two different solvent oils with the following properties:

24.5 Weight -9 * Wt .- $ 6 25.5 Weight * 50 Weight -4 » 34τ * Wt.-ft 26.85 weight-9t 48.9

Table X Mixture A Genetically B Characteristic values 2.5 3- ASXH color 108.1 113.5 Viscosity at 37.8 ° C, east 7.95 8.38 Viscosity at 98.9 ° 0, east 44 11th Viscosity index track track Acid Aahl 0.942 0.942 Diohte at 15 ° C 214 208 Flash point (open cup), ⁰ C 65.2 65.8 Aniline point, ⁰ C 31 31 Aromatic carbon, wt. ^

- 16 -

Q09829 / 1277

Example 4

From a wide-cut fraction of solvent · - eitrakten and the fraction boiling at Atmosphärendruok above 300 ° C residue of a crude oil is produced, a mixture "are recovered from the various then by distillation fractions that are hydrogenated separately" The characteristics of the components of the mixture can be found in Table XX.

- 17 -

009829/1277

O O <O OO

jjeaairerte

Monte fesi 15 ° C

(open beoher),

Viscosity at 37.8 ° C, oSt Viscosity at 98.9 ° C, oSt

S & oresahl

Aailia point, ⁰ C.

uaffiag of traction, ToI

Aromatic carbon, wt-96

3? Ar & f £ inisoher carbon, GtW .- ^

Vaphtheniaoher Carbon, wt. ^

Table XI Extract from
the easy one
Tia Juana-
Deatillate Extract from
the middle one
Tia Juana-
distillate Extract from
the heavy one
Tia Juana-
distillate Backlog of
Tia Juana Raw
oil (bp> 3OO ° C) 0.972 1.003 1.001 0.982 182 235 278 230 34.3 838 not measurable - 4.15 18.75 108.58 34.51 1.0 2.84 3.2 τ, 3 19th 24 -. 88 11 # (41-52) 16.5 St (52-68.5) 7.3 * (68.7-76) - 39.5 36.2 40 30th 45 42.2 40 52 15.5 21.6 20 f
cn 18th

The mixture is composed as follows: Still residue 40

Extract from the light distillate 55 Extract from the middle distillate 20 wt. Extract from the heavy distillate 5 wt.

The mixture is separated into three fractions by distillation. These fractions have the following properties: m

Ms 35 ToI .- * Table XII at
9 ° E, cSt Aniline-
point, O 4th until 55 ToI viscosity
37.8 ° C, cSt 98, 48 5 fraction
Tone 8 Ms 80 YoI .- * 24.2 9.7 48, η 35 141 28.7 47, "55

The first fraction is made under the following conditions catalytically hydrogenated:

Temperature, ⁰ C 300

Bridge, bar 60

Borehole rate 0.4

Hydrogen supply rate 300

Number of steps or passes 1

.. ig -

009829/1277

The solvent oil obtained as a product has the following properties:

color according to ASSM 1

Viscosity at 37.8 ° C, cSt 26 Viscosity at 98.9 ° 0, cSt 3.87 Viscosity index under Hull

Acid steel 0

Density at 15 ° C 0.923 Flash point (open cup), ⁰ C 164 Aniline point, ⁰ O 55 Aromatic carbon, wt .- ^ 30 acperatttr, C-48

The second fraction is hydrogenated under the same conditions as the first traction and results in a solvent oil with the following properties:

Table XIII Characteristic values Solutions! ttel & L

color according to ASTM 2.5

Viscosity at 37.8 ° C, oSt 110.6 Viscosity at 98.9 ° C, oSt 7.88 Viscosity index

Acid number

Density at 15 ° 0 0.948

flaan point (open cup), ⁰ C

20 -

009829/1277

Table XIII (continued) Characteristic values Losungsnittelo "!

Aniline point, ° C 54.6 Aromatic carbon »wt. 56 32 Stook point, ° 0 -33

You third faction will be on the same terms hydrates like the first traction and delivers as a product «in Solvent oil has the following properties:

Table XIY Characteristic values JLBsungsmittelBl

color naoh ASXH 3.5

Viscosity at 37.8 ° C, oSt 494t5 Viscosity at 98.9 ° C, cSt 18.48 Viscosity index 0 Acid number trace Diohte at 15 ° C 0.951 Flash point (open cup), ⁰ C 242 Aniline point, ⁰ C 54.6 Aromatic carbon, wt. # 32 Stook point, ⁰ C -24 Example 5

The starting materials are a light and a medium distillate from a Tia Juana hollow oil, a 25-roll extract from a medium distillate of Tia Juana hollow oil and a

- 21 -

00982 9/1277

44 Yolo-iger extract from a heavy distillate dee TIa Juane crude oils «For the properties of the raw material, see in table XT.

ο ο

CM K \

σι

(D

ο σ »

in

a>

CM

CM

K \ I

KV

KV CU

in r-

ω co

CM «« fr CM

CM

Κ \

cn in CO

\ D I «-CM

in

in

cn m ι ο

t- · ιη CMi \ οιη ι

«K

to

KV

CM

egg

οι

in νο ω

(D r ~ KV TC- CM

4 »4» QQ I »O O

O O O O

O O

»Co cn

"*> CM

in

H t

O CMI

kv cn C?

φ Λ χβ

8. · Ή Ή

■ · 1 I

"rf ^ t

* - cn in cm

· ■!

β «

- 22 - 009829/1277

16 * 5734

(a) Ea a geeiech is produced that consists of a light distillate from Tia Juana crude oil and 65 GeWo-9 & from an extract from a middle distillate of Tia Juana crude oil. The mixture is distilled and the _{traction passing over 10 to 90 tol C} "5t is hydrogenated under the following conditions:

Temperature, ° 0 320

Pressure bar 60

Duration of set speed 0.4 Hydrogen supply

speed 300

Looked! τοη levels 1

The hydrogenation product is a solvent following properties:

Table XYI

Starting values ___ ^ according to (a) solution means Cl

Color according to ASSf > 8 3 ▼ isosity at 37.8 ° 0, oSt 189.6 110 Viscosity at 98.9 ° 0, oSt 10.6 7.65 ▼ iscosity index <o <o Acid88hl 1.4 0 Density at 15 ° C 0.978 0.964 Plasma point
(open cup) «0 234 196 Aniline point, ⁰ C 50 51.8 Aromatic coals
fabric, wt. $ C 35 33

- 23 -

009829/1277

(b) A mixture is prepared which gives 35 aua a deep-fried distillate of a Tia Juana crude oil, too 30 pounds by weight from a complete extract from a medium Distillate and 35 wt .- # from a 44 vol .- ^ igen extract a heavy distillate of Tia Juana crude oil, «This Mixture is distilled and the 10 to 90 vol .- # over-

Temperature, ⁰ C Characteristic values following) 300 Pressure, bar color according to ASTH XVII 60 Viscosity at 37.8 ° C, cSt Output
mixture (b) 0.4 Viscosity at 98.9 ° 0, oSt not measurable 300 Thermoset speed Viscosity index <* » 1 Knowledge supply
wind speed Acid steel 24.4 Number of stages Density at 15 ° C 0 The results are the Flash point
(open cup), c 2.2 Solvent oil Tabel Aniline point, ⁰ C 0.982 4.5 Aromatic coals
fabric, weight, "$ 262 598 60 18.98 32 0 0 0.971 240 62 30th

- 24th

0 09829/1277

Solutions prepared according to the invention!
Particularly stubborn production of sehnierfetten or metalworking oils! ^ also for the softening of rubber and similar substances as well as for use as agricultural spray oils.

00S828 / 12fT

Claims (1)

H 1205 te Εββο Standard Sooiete Anonymous Franeaise Claims Claims Process for the production of solvent oils -which increased aroma content, in which at least two directions are produced from one crude oil and from one of the fractions in aromatic Sbhlenwaaseratoffen rich extract oil g® ~ asn «rivtL, dadtiron 'denotes that the Bztr ^ ktSl bit a tar oil fractions Temisoht and the Sxsowi® dis UlfraktionCen) -rsr or after the Tersiaohen will" 1 »bt * tes are three t know, ißäs ^ oh gskeimiehnetp that an seere-soffea iraloh «Sxi ^ sktöle from ainde» ic.} '* i 5f3f Λ? ·· * ι ^ Η% η <ΐΏ j ·; · "?" ^ asn and before odtu after the ^^ lXi ^ »o * sü other Olfink- 3 ο method according to claim. 1 or 2, characterized in that that distillate © are used as oil fractions » 4 ", method according to claim 1 Ms 3" characterized in that that a distillation residue of a topped crude oil boiling at atmospheric pressure above 300 ° C is one of the oil fractions is used 5 ο method according to claims 1 to 4 # thereby marked, that the hydrogenated Gesisoh from extract oil (s) and oil fraction (s) is processed by distillation to one or more oil fractions old with an increased aromatic content « 6o method according Anspruoh 1 to 5, characterized gekennselchnet that a mixture of 30 to 80 wt _o - $ Eitraktöl (s) and 70 to 20 parts by jC oil fraction (s) is prepared _c 7 · Method according to claims 1 to 6 »characterized by that the hydrogenation is carried out at temperatures in the range from 250 to 400 ° 0 " 6. The method according to claims 1 to 7, characterized in that that the hydrogenation is carried out at pressures in the range from 20 to 80 bar «. 9ο method according to claims 1 to 8, thereby kennaeiohnet, that the hydrogenation with a Durohsata speed of 0.3 up to 0.9 parts by volume of oil per part by volume of catalyst is carried out per hour ο 0 09829/1277 16457S4 10 ο Yerfahren naoh claim 1 toie 9t thereby gekexms ^ iobxut, daae the hydrogenation at Erlner VaeeeretoffsufUh digkelt τοπ 100 him 500 Rauateeile Waeeeretoff (ITPo) J · Ol is carried out « 009829/1277