DE2426411C3 - Process for the production of monohydric and polyhydric alcohols, their ethers and esters and oligomers - Google Patents

Description

1. Process for the production of polyhydric alcohols, their ethers, esters and oligomers 5 and optionally also alkanols by converting carbon oxides and hydrogen into Presence of a rhodium carbonyl complex as a catalyst, characterized in that that one uses a catalyst in the form of a rhodium 10 carbonyl cluster compound, which in the infrared spectrum intense bands at 1868 ± 10cm ~ ', 1838 ^ 10cm-' and 1785 ± 10; cm- ', under pressure of at least about 35 ata.

2. The method according to claim 1, characterized in that 15 draws that one dissolves the catalyst; in one Solvent or applies on an inert carrier.

3. The method according to claim 1 and 2, characterized in that one carries out the reaction at a pressure of about _z0 35-3500 ata.

4. The method according to claim 1 to 3, characterized

_K S.; Stortrttnth
Methane according to the equation

CO + 3 H ₂ ^ = - CH ₄ + H ₂ O

•, C here progresses from left to right at is suitable, i.e. from ππκ ^ ^^ ^

Temperatures below * wa JJ (KikOh

^{se for} rtW 'alcohols have hitherto _essentially been obtained polyvalent acono.

can only be achieved by oxidanone from P ^ _{of crude oil)}

tr ^ «- = _& - _tr de, Esbe _S , eh, hence the urgent need
- ■ the ones to

ien

"S""al50bis300-C.imbeso _n d = _re

WlSLHCM ClHO 4.U. 1 ".." . . 11

6. The method according to claim 1 to 5, characterized in that there is a cluster compound used with an external ion as a catalyst

7. The method according to claim 6, characterized in that a catalyst is used whose outer ion is an organic ligand. 3 <

8. The method according to claim 6, characterized in that that a catalyst is used whose external ion is metallic or non-metallic Cation is.

now relates to a process for r aliphatic alcohols,

vls-products ■ <"" ... """- - · · · -. · ■ = -. methanol and ethanol propanols whose α PciPr at all that ^he go to the erfindungsgemäi _e S ^e Ve ^U r ⁿ e. ? h ^{n e} s a.ten products contain Koh.en-

^^ flZ ^ lT ^^ Ln and carbon oxides t of a rhodium carbonyl complex

2 =

It is known that monofunctional Verbindun-Haufenvefb inventions (cluster compounds) of this IR HautenverDinuu ^ ^^ _React i _on or temperature range w _{unterha [b} ^ _{Reaküo "s n} Bedi conditions

insane

»The Ο-« g-

compounds through reaction of formaldehyde, carbon monoxide and hydrogen obtained in the presence of a hydrogenation catalyst. It is also known

Produce formaldehyde by ^U ™ f ^ ™ "carbon monoxide and hydrogen at elevated pressures,

however, various attempts at formaldehyde synthesis have not yet led to success in substantial quantities. It is generally recognized that the previously published processes for the synthesis of formaldehyde from carbon monoxide and hydrogen at higher pressures are either completely impracticable or lead to unduly low fo ™ ^alde ; y ^da " ^s _p ^b _a S". From GB-PS 6 55 237 is * β reaction CO + H ₂ at elevated temperature and high pressure

_.._ opUH »! over 1500 atü and temperatures ms Sffi £ - at dn hydrogenation ^ u ^ o, ice cream:"

at « > limited groups of meta lato

fenvero ^ metal / metal cover completely

JJ ^ JJ ^^ _{or at least} est to be held together in a naming * share although also th. " _{Atoms dearly} ," the heap

e.mge ^ ^ _Rnodiumcarbo nyl-house

^ Jf _{"is a rhodium} n rhodium bound

^ ^ve ™ 2 " _an ferrous metal such as cobalt and / or indium," to ^ ane.n and ^ _{Rhodi / Rh dlum B} , n-

^^^ ",. Sometimes contain this connection. ^ ung ^ w ^ ^^^ _{| n porm de carbonyl} .

give CO. the "terminal" can be an edge 8J ^ _ke ; _{d and / or} bridging over the area. _can hydrogen

^{l> c} r., .. _{n ff ™ _tn -, e are available. Usable Rhodium

^^ SSin Fig.7d "rges, * e"

24 26 41 I.

Rhodium carbonyl cluster ions with the above infrared spectrum lead with carbon monoxide and hydrogen to the formation of polyhydric alcohols, etc. The The exact mechanism by which these cluster compounds catalyze the reaction is not yet available completely cleared up. However, it is believed that the response depends on the existence of the following Equilibrium:

2Rh ₆ (CO) ₁₅ H "

H,

The clusters are ionic and can come into contact with ions of a different algebraic sign, that conditions prevail under which the rhodium carbonyl heap compound above infrared spectrum is present.

The (outer ion) rhodium as such comes as an ion with the opposite charge. Hydrogen, ammonia or mono- or polyvalent metals as well as a large number of organic compounds, which are known as ligands referred to, in question.

The alkalis (lithium, sodium, potassium, Rubidium, cesium), the alkaline earths (beryllium, magnesium, calcium, strontium, barium), scandium, yttrium, the Rare earth metals (cerium, praseodymium, europium), titanium, zirconium, hafnium, manganese, rhenium, iron, ruthenium, Osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, boron, aluminum, Gallium, indium and thallium in question.

Organic external ions can result from the complex formation of organic substances with the Ousterionen originate or they are ionically bound to the cluster.

The term "complex compound" is applied to coordination compounds obtained from one or more electron-rich molecules or atoms that exist independently with one or multiple electron-deficient molecules or atoms that also exist independently. These organorhodium carbonyl cluster complexes arise through association of organic ligands to rhodium carbonyl in Solutions.

Useful organic ligands contain at least 1 nitrogen atom (hereinafter referred to as the Lewis base nitrogen atom referred to) and / or at least 1 oxygen atom (hereinafter referred to as Lewis base oxygen atom designated). These atoms have a pair of electrons for the coordinptive bond of the Rhodiums. It is appropriate that the organic ligand has at least 2 Lewis base nitrogen atoms or has at least 2 Lewis base oxygen atoms or at least one of these atoms. Such Ligands form chelate-like structures with the rhodium. According to a special embodiment the organic ligands contain 2 to 4 Lewis base atoms, preferably 2 to 3, in particular 2. These Organic ligands can be used in terms of whether they have 2,3 or 4 Lewis base atoms for the hhelate structure containing rhodium.

Organic ligands containing at least 1 Lewis base nitrogen atom, are often referred to below as organic nitrogen ligands, analogous to the organic oxygen ligands. Ligands which both Containing a Lewis base oxygen and nitrogen atom can also be used as organic denote aza-oxa ligands.

The suitable organic nitrogen ligands generally contain carbon, hydrogen and nitrogen atoms, and the oxygen ligands contain carbon, hydrogen and oxygen atoms. Analogously, the azo-oxa ligands contain carbon, hydrogen, Rh ₁₂ (CO) K ²

Oxygen and nitrogen atoms. The carbon atoms can be acyclic and / or cyclic (aliphatic, cycloaliphatic, aromatic including condensed ring systems and those via bridging) being; those with 2 to 20 carbon atoms are preferred. The nitrogen atom can be in the form of a

Imino-N =, amino-N- or nitrilo group N =

exist; imino and / or amino nitrogen atoms are preferred. The oxygen atoms can be called hydroxyl (aliphatic or phenolic,

Carboxyl - \ - COH j,

Carbonyloxy- ^ CO-J

(°
or carbonyl group - II -

are present. In this regard, the "hydroxyl oxygen" is in the carboxyl group and the "oxy oxygen" in the carbonyloxy group the Lewis base atom. The organic ligands can also contain other atoms and / or contain groups such as alkyl, cycloalkyl, aryl, chlorine, thiaalkyl, trialkylsilyl groups or like that.

Examples of organic nitrogen ligands are:

Ν, Ν, Ν ', Ν'-tetramethylethylenediamine,
Ν, Ν, Ν ', Ν'-tetraethylethylenediamine,

Ν, Ν, Ν ', Ν'-tetra-n-propylethylenediamine,

Ν, Ν, Ν ', Ν'-Tetramethylmethylenediamine,

Ν, Ν, Ν ', Ν'-Tetramethylmethylenediamine,

Ν, Ν, Ν ', Ν'-tetraethylmethylenediamine,
Ν, Ν, Ν ', Ν'-Tetraisobutylmethylenediamine,

Piperazine,

N-methylpiperazine,

N-ethylpiperazine,

2-methyl-N-methylpiperazine,
2,2'-dipyridyl, methyl or

ethyl-substituted 2,2'-dipyridyl,

1 A-diazabicyclo-ß ^ joctane,

methyl substituted

1,4-diazabicyclo- [2.2.2] octane,
Purine,

2-aminopyridine,

2- (dimethylamino) pyridine,

1,10-phenanthroline,

Methyl substituted 1,10-phenanthroline.
2- (dimethylamino) -6-methoxyquinoline,

7-chloro-1,10-phenanthroline,

4-triethylsilyl-2,2'-dipyridyl,

5- (thiapentyl) -1,10-phenanthroline.

Examples of organic oxygen ligands are:

Glycol, methoxyacetic, ethoxyacetic, diglycol, Thiodiglycolic acid, diet ether, tetrahydrofuran, dioxane, tetrahydropyran, catechol, Citric acid, 2-methoxyethanol, 2-ethoxyethanol, 2-n-propoxyethanol, 2-n-butylethanol, pyrogallol oxyhydroquinone, 2,3-dihydroxynaphthalene, cyclohexane-1,2-diol, oxetane, 1,2-dirnethoxybenzene, 1,2-diethoxybenzene, Methyl acetate, ethanol, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-di-n-propoxyethane, 1,2-di-η-butoxyethane, pentane-2,4-dione, hexane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, 1 - phenylbutane-1,3-dione, 3-methylpentane-2,4-dione; Mono- and dialkyl ethers of propylene glycol, Diethylene glycol, dipropylene glycol;

Examples of aza-oxa ligands are: Ethanolamine, diethanolamine, isopropanolamine, Di-n-propanolamine, N, N-dimethylglycine,

Ν, Ν-diethylglycine, iminodiacetic acid,

N-methyliminodiacetic acid, N-methyl diethanolamine, 2-hydroxypyridine, Methyl substituted 2-hydrocypyridine, Picolinic acid, methyl-substituted picolinic acid, Nitrolotriacetic acid. ^ S-Dicarboxypiperazine, N- (2-hydroxyethyl) iminodiacetic acid, Ethylenediaminetetraacetic acid,

2,6-dicarboxypyridine, 8-hydroxyquinoline, 2-carboxyquinoline,

Cyclohexane-l ^ -diamin-N.N.N'.N'-tetraacetic acid,

the tetramethyl ester of

Ethylenediaminetetraacetic acid.

Further organic external ions can be formed through ionic association with the rhodium carbonyl cluster ions. They are formed from organic compounds, the Lewis base nitrogen atoms contain and are composed of carbon, hydrogen and nitrogen, for example piperidine, 2-methylpiperidine, 3-methylpiperidine, pyridine, 2-methylpyridine, 4-ethylpiperidine, triethylamine, benzyltrimethylammonium acetate and formate, tri-n-butylamine, dibutylamine, Methylamine, dodecylamine, morpholine, aniline, benzylamine, octadecylamine, naphthylamine, cyclohexylamine.

The F i g. 1 to 5 bring infrared spectra between and 2400 cm- ^{1 of} a number of rhodium-containing compounds.

The spectrum in FIG. 1 relates to rhodium carbonyl-2-hydrodypyridine, prepared by adding 4 moles of 2-hydroxypyridine to 1 mole of rhodium in the form of Rh (CO) 2-acetyloacetonate in a magnetically stirred autoclave in the presence of carbon oxide and hydrogen a pressure of 738 ntü and a temperature of 21O ⁰ C.

The spectrum of Fig.2 relates to a Rhodium carbonyl heap compound obtained from 4 moles of piperidine and 1 mole of rhodium dicarbonylacetyloaectonal under the above process conditions.

The infrared spectrum of Fig.3 relates to Rhodiumdicnrbonylacelylonctonnt, which in the magnetically stirred autoclave in the presence of carbon monoxide and hydrogen under the above conditions was held.

The IR spectrum of FIG. 4 corresponds to the substance ims I * i g. 2, but that this is under a gas pressure from 1260 utü was obtained.

The diagram of Fig.5 relates to a

Substance which, as a modification of the substance from FIG. 1 has been obtained at a gas pressure of 1260 atm.

In these above catalyst preparations, the solvent or diluent was dimethyl ether of tetraethylene glycol (tetraglyme) and the catalyst concentration was 1% based on weight of the existing rhodium.

In the spectra of Figures 1, 2, 4 and 5, the absorption bands 1, 2 and 3 may be den

ίο to be ascribed to corresponding equilibrium products according to equation I. The intensity of these absorption bands in FIG. 4 and 5 is possibly due to a greater concentration of Rhi ^ CO) ^ - ² in the reaction mixture compared to the spectra of FIGS. 1 and 2. The absorption band 4 of the spectra 1 to 5 could be assigned to dissolved carbon dioxide and band 5 to dissolved carbon monoxide. Band 6 in Figures 2 and 4 is possibly the frequency of the stretched carbonyl from N-formylpipe ridin.

All examples of the spectra from FIG. 1,2,4 and 5 are characteristic of a system which leads to good yields of polyhydric alcohols such as ethylene glycol. The spectrum of Fig.3 shows the

Absorption band 7, which can be assigned to the frequency of a bridge carbonyl in the neutral complex Rh ₆ (CO] Ii _6. In this example, the conditions are not sufficient to bring about an equilibrium in the sense of equation I. However, will the pressure in the production of the substance on which FIG. 3 is based is increased to 1760atü, thus achieved an equilibrium in the sense of equation I.

In FIG. 6 a test arrangement is shown schematically which is used for determining the existence of Rhodium carbonyl heap compounds with the above infrared spectrum during the production of polyhydric alcohols within the meaning of the invention Process is suitable.

The reactor 'I is with the IR analyzer 3

connected; the analyzed sample is collected in the collecting vessel 21. The reactor 1 consists of an autoclave lined with corrosion-resistant steel and having a volume of 150 cm ³ . It has a magnetic stirrer device in order to

the ability of a gas leak to be kept low. The reactants are discharged via line 2 with a shut-off valve fed. The reaction partner is brought in with an injection needle from a sleeve from corrosion-resistant steel and a rubber Plug. After the onset of the reaction, samples become taken through heated line 4 when the reaction has reached a point of analysis it is asked for. But you can also continuously take samples from the moment the reaction occurs temperature is reached. One shouldn't try that Line 4 to open, close and open again. This could lead to a depletion of carbon monoxide and Lead Ausplattici'cn of the catalyst metal in the infrared measuring cell. The withdrawn from reactor I.

Oo sample arrives via the heated line 4 with valve S, which is measured at 2100 atmospheres, further through heated line 13, a heated intermediate sample valve Il and heated valve 15, also designed for 2100 atmospheres, in the infrared analyzer 3. Should irgcndwcl-

(15 before problems occur in analyzer 3, you can use With the help of valve U, line 13 is shut off and excess product via line 7 at valve 9 be drained.

A Perkin-Elmer spectrograph was used as the IR analyzer. The product entered a high pressure, high temperature cell where the scanning takes place. This cell is also designed for a pressure of at least 2100 atti and temperatures of up to 250 ^° C. The window of the cell is appropriately sealed in order to be able to withstand such a high pressure. The infrared spectrograph cell is the subject of another application. The analyzed product leaves the cell via line _{16,! 0} valve 17, dosing device 19 and collection vessel 21, valve and Dispensers are also designed atm for 2100th

^{The solvent (100 to 130 cm 3} ) used for the reaction is placed in the reactor 1 and then CO + H ^{2 is introduced} up to a pressure of about 200 atm, the valves 5 and 15 are open in order to build up pressure up to the analyzer 3 reach. Valve 17 is then opened and the meter 19 is adjusted so that a small current flows through it to ensure that the valve U is not closed. About 30 cm ³ are passed through the system, then valve 17 is closed, the whole thing can now stand for 15 minutes to ensure that an initial seal is achieved on the cell (determined by the fact that no solvent visibly escapes from the cell) . The cell is then opened, valves 5 and 15 closed. The reactor 1 is then drained and reloaded with catalyst dissolved in 130 cm ^{3 of} solvent. Then the reactor is put under pressure again - 200 atü CO + H2 - and connected again to the cell by opening valves 5 and 15. The gas leads to a pressure rise to a value of the Va at the reaction temperature of 210 to 22O ⁰ C the desired operating temperature.

If you only want spectra under reaction conditions, the reactor 1 is first heated and brought close to the reaction temperature before the lines 4 and 13 and the cell 3 are heated. If spectra are also to be recorded at temperatures below the working temperature, the reactor, the cell and the lines are brought to the desired temperature at the same speed. Flushing the reactor and through the cell begins at room temperature. The various switches for the analyzer, scanning and the like are housed in an external control block for safety reasons. Due to the flow from the reactor to the cell, a spectrum can be recorded at any time as soon as the reactor, lines and cell are at the same temperature. The flow through the cell is adjusted to about 1 cm ³ / min. The volume of the entire system from the reactor to the metering valve is about 10 cm ³ , so that a spectrum can be recorded every 10 minutes if necessary. Generally, the reaction conditions are maintained for about 30 minutes while 3 to 4 spectra are recorded. CO + H2 are fed to the reactor to maintain a constant pressure during the passage of a continuous sample through the cell. The whole thing is then slowly cooled; spectra can also be recorded during this cooling period. When the system has cooled down ^{to 120 to HO 0 C.} all valves are closed.

The term "carbon oxides" used here means carbon monoxide and mixtures of carbon dioxide and carbon monoxide understood. They are introduced into the reactor as such or formed in situ therein.

In the process according to the invention, a normally liquid organic one is generally used Diluent applied; they can be inert or reactive; they can use the above organic ligands or mixtures thereof. Examples are saturated and aromatic hydrocarbons (hexane, Octane, dodecane, naphtha, decalin, kerosene, mineral oil, cyclohexane, cycloheptane, alkylcycloalkane, benzene, Toluene, xylene, naphthalene, alkylnaphthalene), ether (tetrahydrofuran, tetrahydropyran, diethyl ether, 1,2-dimethoxybenzene, 1,2-ethoxybenzene, mono- and Dialkyl ethers of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, dibutylene glycol and Oxyäthylenoxypropyleneglycol), carboxylic acids (acetic, propionic, butter, capric, stearic, benzoic, cyclohexanecarboxylic acids, alkenols (methanol, ethanol, propanol, isobutano !, 2-ethylhexanol), ketones (acetone, Methyl ethyl ketone, cyclohexanone, cyclopentanone), esters (methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl butyrate, methyl laurate), Water, anhydrides (phthalic anhydride, acetic anhydride). Tetrahydrofuran, dioxane and the like are preferred Mono- and dialkyl ethers of triethylene and tetraethylene glycol. The use of reactive diluents in carrying out the invention Process can lead to a number of viable products. So you get mono- and diacetic acid esters of ethylene glycol by using Acetic acid as a diluent. The use of alkanols, such as methanol or ethanol, leads to the Monoalkyl ethers of ethylene glycol.

The amount of catalyst is not critical and can vary over a wide range. In general, the process according to the invention can be carried out as desired in the presence of a catalytically effective amount of active metal compound, preferably rhodium compounds. The reaction already takes place at only 1 × 10 ⁶ wt .-%. Even smaller amounts, calculated in terms of rhodium metal based on the total weight of the reaction mixture, are effective. The upper concentration limit can be very high, for example on the order of about 30% by weight rhodium and above. The practical upper limit arises from economic considerations in view of the excessive cost of rhodium metal and compounds. There are no particular advantages with relatively high concentrations of rhodium. Depending on various factors such as the nature of the external ions, the partial pressure of carbon oxide and hydrogen, the working pressure of the system, the working temperature, the diluent used and other considerations, a catalyst concentration of about is generally required for carrying out the process according to the invention

1 x 10-'is x 10-% by weight Rh

in the catalyst, based on the total weight of the reaction mass, is desirable.

The working temperature can fluctuate over a much higher temperature range. In general, the process according to the invention is carried out at from about 100 to 375 ^° C. and above. Working temperatures in excess of this do not belong to the preferred embodiment of the process according to the invention. At lower temperatures, the reaction rate is noticeably slower. At higher tempering

709639/367

It can already lead to a certain in & lialbility of the Catalyst-coming u Not nevertheless the Reafc is running soaked in polyhydric alcohols and / or their Derivatives. In addition, the geeket weight restriction for ethytettgtykol ^; - 5s

2CO Hh 3H ₂

HCKM ₅ CH ₂ OH

to

Note ζω '. At relatively high temperatures, the equilibrium is increasingly carried over to the itike! Jette of the equation «. In order to increase the yields of ethyl fat glycate in the reaction to area, higher parts pressures of co-memoxide and hydrogen are required. Processes with high operating pressures, however, are not preferred execution forms of the process according to the invention in view of the high investment costs required due to the high pressure system required! «D their operation. Suitable work "sitemneratuirenswal50bis3 ^ dere 19ObRlTS ¹ C a"

The implementation is expediently carried out with high pressure over a wide area under about 35ata IBnRn reaction speed too low; higher reactivity opportunities and / or higher degrees of unsaturation can be achieved with as higher working pressures, for example for Beäpid zumimillest 55atar> uckebäshina ^ to.35eOatffikräinn ^ aiBgewaiiidt

door th. the

Shares

koMeminonmud)

.w about 10

ία «particular about 5: 1 in I _: 5L

^ v «and Wav κηίοΠ m bOdn fortune, kfcmrn. «MeHc dta. Gas mixture «» are applied; which jMbcft, to, Emm MMMl dter tew »« ·. A ^ togslbrm, dta, rfdeneB method *> »d Man Hm zmh from > **** +

sä

wise,. halikMiMwinhch eder konimwefI

I have more advantages, the mcto dmch due for it Required komtrokuven Auiwenuuugen be comensated. According to a method of operation according to the invention, one reckons with buckets maximum pressure of about 175OmSl KosleranMÜStg It is advantageous to print less than about 100,000. esponclc ^ under about 42OaE ^ En b ^ ücMMm-Dnfl ^ berendj places ZWBCbCDι about 70 and MOatü bei düeseiD

Hydrogen and Carbon Oxide In the preferred embodiment of the inventive method, the rhodämikatysator is in lamb; in the liquid Rkd ^ dh

DwVerwaizeitlMaderAuction of the invention ^^ A moderate procedure can be between Mknuten and some

about two and a half hours and the administration to a moderate extent by the elderly

^ p des Kat ^ », _MS . of

p and the type of Verdtoeng- "

55,

ίο

wad although in a single reaction zone or a plurality of reaction zones, in parallel or in series or also intermittently or continuously in reaction rotors or a number of soft zones one behind the other. The constraint material of the plants should be ffli The reaction does not take place in the course of the process resist. The reaction zone could be provided with buckets of the inner and / or outer heat exchanger. to regulate the temperature as required and to prevent the exothermic reaction from running away. In the preferred embodiment of the process according to the invention, stirring can also be used provide, for example by shaking, shaking, with i Rh

bucket stirrer, by Schwi

Ultrasound or

G,

the same. The catalyst can initially be introduced into de Reaktüottszome or is fed in continuously or intermittently during the synthesis reaction.

As already stated above, the working conditions can be enhanced by the rules of the Atbyteng% kolkoozenitration ISr optimal implementation UnxMor weakness of the invention Procedure. In the case of the contemporaneous process, if if one prefers to work hetsptefewense with a relatively low conversion, it is generally the case wüisscfaeiiswert. to circulate unreacted synthesis gas given MB with fresh gas. the

Weer. like ααπΓ & ^ Ιήη. Fractionation. Biirak tion or dergfekfceis. A fraction containing the Rbod & mÄatalysator in general in emem

Nbtok d

y Bg

Subpnxtokt umd / or m the VerdunnungsimttdL can be röckgefiaart. But this group can completely or teüweise amfgeaiibetet or * Rtndiumgehah again the KataHjutor be regenerated Fresh catalyst can the RfitekSaufstrom for "overall" ^ "** ^ ^1" introduced * ¹¹ ** ■ Reaktiomzone

will.

With the method according to the invention one can idfcwett ^

anticipated Ausilteungsform one increases with Reactronical rhodromcatvsators ffite excellent results. The synthesis of multi-value

* "* ^ADkohoBraB " ^ ⁰ *** ⁵ ^ "" ^{Dvnvmc mm} *** ^but

"Wk with catalysts dtodrfihren," fe in the reaction medium not dead homogeneous venafe simdL hard d

or fixed cata ^ torenimSSS ^ and / or gaseous Medüen ^ t ebohb g «^ T in one Ai S

Apply UmaM , s » hmm * e

like TiDMide. AkmJwyülli Kuesel ^ l activated carbon TManeide. ZMiwenfe. Z ^ LJTkTL Art on

Wise ter ^ ateffi «

dta »i. the t

you vorWdo. and ^ ** m «ber

KoMenmoMmid dfe as

connecting passage. Examples of substances containing rhodium, which mam can bring directly into the synhesis zone.

are ■ · "'■' ■. ■ · ■ '■■ ■ ■ ■■' ■■ ■

Tia ^ OTftccfiinndodecacarbonyl, DöriiodSunoctacartonyL HexariDodüennhexadecaca BBnmiftimii (H) -ptoptonat, R & edniffln (ll _r butyrai. Rfa> dmm (ll) -valerate. RkM & om (IIl> naphthen3i. RhodSmmficarbonylacetylacetonat, RbodnimDt-tiri ^ acetylacetonate ^ RbfMfiomtnriiqfdroxid.

RlEodmiBdkarbonyi (l-phenylbutane-13-dione) L dh (X

12th

In the production of these variants, one can calculate about 100 to 20 mol for the substances forming the atiSenroiieti per mot of rhodium β of the RlMäiiTsiverfoverbindungen. Other ratios can also ksam user-

S the, especially if it wSmdtcroweriencIieint the the AuBenkMten Wderadem Venlbractag.eiii] io quantities of a dilute side ice is included in the L

The solutions of the knives Ikatalytisdiii are effective Rhodium compounds, .kömpooi on .. ", ennent. Porous The carrier - as explained above - is dismissed For example, the Kalaiüssatortösurtg, on a Cast carrier or the carrier in unnecessary Solution gelaiidit, whereupon the Übeirscteß is cleared. The impregnated carrier «U dlatrn on honors such

The temperature 'got a d'affi dlas, Verdümnuicigsmiltet evaporated. Vacuum rubber can be attached.

In the followingic Betsfwetom beziiehea skh the Information on parts on the GcwkM fe> DCc »Effectiveness« results from the »following GUcicfaang:

Effectiveness «%> =

fair rhodium. Rhodium and rhodjumhalnge VerfeÖKtoamgen on a porous carrier.

The hardening of the Rhodiunicarbonvi-HaufeiDvcrbinduagca usually takes place in an or roeea diluents, such as benzene. Tetrarhodli- ■ mdtodccacsriiony) may because of its limited LüsfitMceätdem diluent in female form g were. In its place one can use one of the above-mentioned rhodnnnbahigen ver large alcohols g flöss% K (BisidiErte

Beuspüel! 1!

OrgaaiK & x: ligands such as 2-hydroxypyridine, and

other compounds which form aaemons may also be used. The reaction to Haufenverbimdomg takes place "beer carbon monoxide pressure, optionally in the form of hydrogen, from about 1 to 15 atm and above at a temperature of about 30 to HW ¹ C in a quote from minutes to a few days, generally in about 30 minutes to 24 hours. The rhodium heap compound contained in the VerdiBBUiiig9mDttel is catarynically effective via iffie processes. It contains the Rbodium in a heap-like combination with KoMewid and the corresponding iuBereti lon.

In a TSO ^ cmt Reafctewr asu "koinrosknis resistant steel fir with Magnetaröferar Eisten pressure M & atm were 4000 2 lmMof Rtodiwiislicairboiiiiybcettylbacetonat and 12 mM 2-t © rrnftne" t5pijiriidSmi dissolved 75 g m

3 © Dimethyl ether from TesraStiirjtagitykQll used and synthesis gas in a MoJlwrfiäilllims H ₂ : CO = 6JM40 to 1000 atmospheres heated in the wound mf 22StC and at this Betrtetotempeiiaai the pressure arf 1333 alü increased. This ArfcerMieiimgiiinigcrai beckons 4 hours

3IS right, although the Dmmck between 1260 and 1400 atü by NacfaspetBeo) -from Symtdbesegas. Dec entire Dnrcfcabflal wäünrearoll the reaction was atü 1180, the ReaktorönfeaTt tamme äxxm aiuf Rammtemperatur abkühten _v äfoerschrasiige gases wunrdem abgebla- sen and lOljB g Reaktioospodtofctc anssgetragem. Durd Gas-Russig-CkomatogragiinJe wmdte & m content of 9 g methanol IS g Meifeylicpmrat, (US ÄtasoL 20.4 g ÄthytenglykolL t, 3 g Äl% fet ^ lyikdteiiOiM> £ oirraiiiiat and 2 g glycerine determined

There were (olgemde VaÄtimtrem dwcngdühr unc the values given below should be displayed.

Gu yield

admission

saunted CHiOH Οφβί

aiii EK g.

Gijttrrini

Moraoemftiytatliicr of Triithylen- Hydroxyptpcröin SDO Monona «% <ltther von DiSihykn-HydroxypiiperMlin

Telnu ^ jdniiiinrauni Hydrwiypiperiiilliin 1207

r "on tetralthylene-Pipcridiro 1507

it. 09j AthancA. I g AihinoB.

106JB 7.7 115J 23 94J 4.4 H6v2 3J2 106.3 6 \ fr 213 3.1 «) 114.9 IJA 13.9 07 **

tlykoB

Example 2 β * gjrykol emgwetzt and mt eimewii Syniteseg »*» Motve In dta reactor from example! 1 were 3 mmol of hilUnB Hj: CO ~ 35 / «5i. some Dradc from 1000al RhodimidkcriionylacetytoamoiMt and 12 mmol2-Hy- built up Daum wmrdc to 23TC, where d

dioxyp} ndBjn m 75 g Dhncthylltlher von Tctrailhykn- Druck auf 1333 atöi amti «f. The Dmidt was 2

held between 1260 and 1400 atfi, with 500 atQ gas were recorded. 91.7 g of liquid reaction product were discharged, which contained 13 g of methanol, Contained 03 g of methyl formate, 0.1 g of ethanol, 9.4 g of ethylene glycol and 2.6 g of glycerine

Example 2a

In a modification of example 2, a gas pressure of 500 atm was introduced and the reactor contents were set at 220.degree

increased, whereby the pressure was now 667 atm. This temperature and the pressure were maintained for 2 hours adjusted to 630 to 700 atm by repeated addition of synthesis gas. The entire gas intake was 93 atm. 76 g of liquid reaction product were discharged, of which 0.8 g of methanol and 0.1 g Methyl formate and 2.4 g of ethylene glycol were.

The following variations were carried out and the values given below were obtained.

According to example 2 or 2a

Ligand

Pressure drop

atü yield total

CHaOH

CH ₂ OH

CHzOH

HCOOCH ₃

Piperidine 100

3-hydroxypiperidine 413

3-hydroxypiperidine 60

4-hydroxypiperidine 44.7

4-hydroxypiperidine 67

2-pyridylcarbinol 73

2,6-dihydroxypyridine 180

2,6-dihydroxypyridine 20

2-cyanopyridine 473

2-cyanopyridine 80

2-acetyl pyridine 447

2-acetyl pyridine 80

2-methoxypyridine 500

2-methoxypyridine 100

Di-2-pyridyl ketone 420 Di-2-pyridyl ketone 93

2,6-Dimethoxypyridine 247 2,6-Dimethoxypyridine 13

2-dimethylaminopiperidine 427

2-dimethylaminopiperidine 87

o-anisidine 267

o-anisidine 20

Piperidine 360

Piperidine 47

1,8-naphthyridine 100

0.2 g ethanol, 0.9 g glycerine.

0.5 g of ethanol.

0.4 g of ethanol.

0.2 g of ethanol.

0.5 g glycerin.

0.1 g ethanol, 4 g glycerine.

0.1 g of ethanol.

0.3 g of ethanol.

80.5 3 0.4 0.4 86 2.8 6.1 0.8 79 1.9 0.8 02 87.6 2.8 8.5 0.7 ·) 76 1.7 1.2 0.2 81.6 2.4 1.0 0.2 79.8 0.8 2.1 0.1 ") 75.6 0.1 0.4 - "·) 88.7 3 5.9 0.7 ····) 76.9 1.5 0.2 0.1 82.5 2.8 6.6 0.8 ⁺ ) 76.6 1.8 0.8 - 82.8 1.8 7.9 0.5+ ⁺ ) 78.5 1.5 1.5 0.2 83.2 3.2 5.7 0.9+ ^{+ +} ) 81.8 1.9 0.6 0.2 80.1 1.3 3.8 03 74.7 0.5 0.2 - 85.9 2.8 6.4 0.7+ + + +) 80.1 1.8 1.1 0.2 84.1 1.6 3.4 0.4 73.2 0.3 0.1 - 84.3 3.4 6.0 0.1 79 13th 0.1 0.1 77.2 2.4 1.2 0.2

example

2 mmol of rhodium dicarbonylacetyloacetonate and 30 mmol of magnesium acetate dissolved in 55 g of dimethoxytetraethylene glycol and 20 g of water were introduced into the reactor of Example 1 and a pressure of 930 atmospheres was applied with synthesis gas having a molar ratio of H ₂ : CO = 60/40. Reaction ^{temperature 210 0} C at a pressure of 1200 atm for 4 h, the Pressure between 1160 and 1240 atü by repeated Make-up of synthesis gas was complied with. The total pressure drop during the reaction was 547 atü. Yield of liquid reaction product 84.1 g, of which 6.5 g of methanol, 5.6 g of ethylene glycol, 0.6 g Propylene glycol with small amounts of methyl formate, ethanol and glycerine.

Example 3a

Example 3 was repeated, but this time a synthesis gas with a molar ratio H2: CO of 40/60 applied. The total pressure drop over the 4 hour reaction was 487 atm; Yield 83.8g liquid reaction product containing 2.7 g of methanol, 4.6 g of ethylene glycol, 0.6 g of ethylene glycol monoformate and 1.3 g of propylene glycol.

15 16

The following variations were carried out and the values given below were obtained.

After instead of Mg-acetate pressure from example waste 3 or 3a

atü g

CHaOH Ethylen- Propylen- Glycerin HCOOCHj CiHsO Glykoi Glykol

3 Mg-lactate 480 89 4.2 6.6 1.3 0.4 10 mmol 3 Al-lactate 587 78.5 2.1 7.0 1.6 0.2 10 mmol 3 Ca lactate 560 90 5.9 7.9 0.9 0.3 10 mmol 3 Ca lactate *) 673 89.3 4.9 9.4 1.2 0.1 10 mmol 3 Ca lactate **) 627 93.8 4.3 8.8 1.7 0.1 10 mmol 3 Ca-lactate *) 540 88.2 7.8 5 0.7 10 mmol 3 Ca-lactate **) 580 93 7.7 6.4 0.8 0.5 10 mmol 3 Al citrate 200 73.1 1.8 2.2 0.2 - 3 Mg glycolate 453 76.9 2.3 4.6 1 0.5 3 Al-lactate ') 200 74 2.2 1.4 0.1 - 3a Ce acetate 133 66.7 1.2 2.2 0.7 - 3a U-acetate 313 83.4 1 1.2 1.1 0.1 3 Ba-acetate *) 233 83.2 2.1 2.7 0.1 - 10 mmol 3 Sr acetate *) 87 64.9 1.4 1.1 - - 20 mmol 3 Zn acetate *) 100 73.5 0.9 0.8 - - 20 mmol 3 Na acetate *) 533 90.5 12th 2.4 - - 33 mmoles 3 Na-borate *) 293 77.9 7.3 0.5 - - 10 mmol 3 Na phenolate *) ') 577 88.2 9.8 0.9 - - 12 mmoles 3 Na methylate *) ') 373 82.7 7.2 0.8 _ - 12 mmoles 3 Li-acetate *) 473 88.9 11.8 2.1 3 Cs acetate) 493 83.6 10.9 0.7 - - 3 Cs formate *) 607 82.5 14.7 0.6 - - 3 Cs-carbamate *) 487 87.8 16.2 0.3 - - 15 mmol 3 Cs-hydroxide *) 33 74.3 7.5 0.3 - - 3 Benzyl trimethyl 333 72.2 7.2 7.6 1 0.2 ammonium acetate 20 mmol

0.4 - 0.6 0.6 2.3 0.3 2.1 0.4 0.8 0.6 0.6 0.1 1 0.2 1 0.2 0.4 0.1 0.5 0.2

215 ⁰ C.

220 ⁰ C.

Solvent, 55 g methoxy triglycol + 20 g H2O.

Solvent, 55 g diethylene glycol monomethyl ester + 2Og H2O.

Solvent tetraethylene glycol dimethyl ether.

Example 4

Example 3 was repeated, but in this case instead of rhodium dicarbonylacetyloacetonate and Ma-kesium acetate, Mg [RhI ₂ (CO) ₃₀ ] (2 mmol Rh) was used. The gas uptake was 253 atmospheres; fl reaction product 74.8 g, of which 1.1 g methane ethylene glycol and 0.9 g propylene glycol.

Example 4a

liel 4 was repeated, but in this case as 75 g of tetraethylene glycol dimethyl ether were used. The gas uptake was ; liquid reaction product 72.6 g, of which 2.4 g ιοί and 0.3 g ethylene glycol.

Example 4b
, iel 3 was repeated, but in this case as * ■ TRh ₁₂ (CO) ₃ O] ₃ (2 mmol Rh), was 293 atm; liquid reaction

. _ n_il _ "! Torr Δ ti!, Lan.rl.,

_afnah Ue was 293 atm; liquid reaction ^

₈ 42g, of which 1.2g methanol, 3.8 g Ethylengiy p ^^ yienglykol and 0.2 g Glycenn.

In addition 7 sheets of drawings

Claims (1)

_{In the case of} those on KoWt- Nickel primarily an h ^N and reforming of similar processes are known. The only previously applied patent claims: ™ " ^A " * " ^Μ · * ^ η Beisoielen dei