AU610229B2

AU610229B2 - Homologation process for producing ethanol in a mixture with propanol and butanol

Info

Publication number: AU610229B2
Application number: AU21596/88A
Authority: AU
Inventors: Walter Prof. Strohmeier
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1987-08-29
Filing date: 1988-08-26
Publication date: 1991-05-16
Anticipated expiration: 2008-08-26
Also published as: AU2159688A; BR8804378A; JPH0259533A; JPH0460589B2; EP0305829A2; EP0305829A3; DE3728981A1

Description

rl Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFIT i 1

(ORIGINAL)

Class Int. Class Application Number: Lodged:

B

Cpmplete Specification Lodged: oe So 'Piority

I

o w o Accepted: Published: 0000 a a ooo KFelated Art: a 00 O 04 *Name of Applicant: 0 00 00o o o 00 Address of Applicant: 0 00 So 0 0 Actual Inventor: 0 o0 Address for Service: HOECHST AKTIENGESELLSCHAFT Bruningstrasse, D-6230 Frankfurt/Main 80, Federal Republic of Germany WALTER STROHMEIER EDWD. WATERS SONS, QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: GrN- PROCESS FOR PRODUCING ETHANOL IN A MIXTURE WITH PROPANOL AND BUTANOL The following statement is a full description of this invention, including the best mehod of performing it known to ft St 4 S I IS I 0* 44 44t I

''I

4 r K 14 4 1 /Process for producing ethanol in a mixture with propdnul and butanol The invention relates to a process for producing ethanol and in additjon n-propanol and n-butanoL by reacting methanol with carbon monoxide and hydrogen in the presence of catalysts which contain cobalt and ruthenium.

This reaction is called homologation. Starting from Lhe simplest alcohol, it permits the production of higher homologous alcohols by introducing one or more CH 2 groups.

Homologation is of increasing interest, since it opens an approach to the production of higher alcohols, which is independent of the use of petroleum. The starting materials required are synthesis gas and methanol produced from it; synthesis gas is accessible, for example, from coal or natural gas by various, industrially proven processes.

It has been known for a long time (compare, for example, German Patent Specification 867,849) to convert methanol to ethanol with hydrogen and carbon monoxide in the presence of a water-soluble cobalt catalyst at high temperatures and pressures. This reaction proceeds in accordance with the equation: CH3OH CO 2H 2 C2HsOH and, at the same time, higher alcohols can also be formed to a minor extent according to

CH

3 OH n(CO 2HC) Ci (CH) nOH n Whereas originally cobalt was exclusively used as the catalyst for the reaction, multi-component catalysts have gained increasing importance in the course uf t ime.

US Patent Specification 3,285,948 describes the production of ethanol from methanol with the use of cobalt as the catalyst, iodine or an iodine compound as a first promoter and a ruthenium halide or osmium chloride as a further promoter. The claimed measures are said to lead to an increase in the selectivity of the reaction to give ethanol.

The same object is desired according to the

V-.

i 1 l i' i -2process of German Offenlegungsschrift 2,625,627 by means of a catalyst system which consists of cobalt, a halide as I promoter and a tertiary phosphane; the reaction takes place in a hydrocarbon as the solvent.

According to the teaching of US Patent Specif icdtion 4,133,966, ethanol is obtained from methanol and synthesis gas by the use of a catalyst which consists of cobalt acetyl acetonate, an organic compound of an ele ment from Group VA of the periodic table of the elements, a ruthenium compound and an iodine compound.

The measures described above do not suffice to increase the selectivity of the reaction to such an ex-- S {c tent that it is suitable for industrial application. It t t must be taken into account here that by-products are ob- C C tained not only in a large quantity but in the form of numerous, different individual compounds. Thus, in addi- CCrIIe l tion to the desired alcohols, hydrocarbons such as methane, ethane and propane, various ethers, and also esters, for example, methyl acetate, ethyl acetate and propyl acetate, and acetals such as acetaldehyde dimethyl acetat, acetaldehyde methylethyl acetal and acetaldehyde diethyl acetal are formed. Industrial utilization of the process therefore requires a large outlay which is not always economically justifiable, in order to isolate, by physical or chemical means, those substances which can be used as intermediate and end products from the multi- Splicity of the compounds present in the reaction mixture.

1 VAlthough the selectivity of the reaction can be Simproved by the addition of a solvent to the reactants, this measure entails a considerable decrease in convei ion, relative to reactor volume and time.

A reduction in the formation of by-products without significant impairment of the conversion is achieved by the use of certain phosphanes as a constituent of the catalyst system. Thus, in DE 3,042,434 Al, a process for producing ethanol and n-propanol is described, wherein methanol is reacted with carbon monoxide and hydrogen at 150 to 250 0 C and eLevated pressure. The reaction takes place in the presence of catalysts which contain 3 cobalt and ruthenium as a compound, iodine or an iodiJd and a bidentate organic phosphane or phosphite.

Even though this variant of the homologation of methanol leads to a 'arked improvement in the methanol conversion and selectivity of the reaction, the object remains of improving the process with regard to both teatures.

According to the invention, this object is achieved by means of a process for producing ethanol in a mixture with propanoL and butanol by reacting methanu with carbon monoxide and hydrogen at temperatures from 1800 to 250 0 C and pressures from 20 to 60 MPa in the o 00 o. presence of 0.07 to 0.4 mol of water per mol of methanol °oo and of catalysts which contain cobalt and ruthenium io o; 15 the elemental form or in the form of compounds, iodine o or iodide and an organic monophosphane or phosphite or a 000000 :0 bidentate organic phosphane or phosphite. It is chardc- 6 0 0 S terized in that 0.2 to 4 mol of a cyclic monoether or polyether per mot of methanol are added to the reacti,n .oo 20 mixture.

0oo The characteristic feature of the process according to the invention is the addition of a cyclic monoether 'Oo of polyether to the reaction mixture. Surprisingly, the effect of these ethers is that the conversion of methdiol and the selectivity of the reaction can be further enhanced, as compared with the processes of the state ot 00° the art. In particular, the formation of ethers is 0 4e markedly suppressed. The cyclic monoethers or polyethers are in general employed as a single compound, but it i:.

of course also possible to use mixtures of two or more compounds. Tetrahydrofuran and dioxane have proved to be particularly suitable as cyclic monoethers or polyethers.

An essential aspect of the new procedure is that the formation of ethers is largely eliminated only if the cyclic monoether or polyether is used together with calalysts which contain organic monophosphanes or phosphites or bidentate phosphanes or phosphites. Furthermore, it is possible to exert an influence on the proportions of 4ethanol, propanoL and butanol in the reaction product by varying the reaction conditions.

0.2 to 4 mot of the cyclic ether soluble in thu reaction mixture is employed per moL of methanol. It has proved suitable to use 0.3 to 3 and especially 0.5 to mol of cyclic ether per moL of methanol.

The cataLysts used for the process according to the invention contain cobalt and ruthenium, and also ioudine or iodide and furthermore an organic monophosphane or phosphite or a bidentate organic phgsphane or phosphite.

Cobalt and ruthenium are used either in the elemental form or as compounds. Under the reaction condiget* tions, they are converted into carbonyl or hydrocarbonyl *4 4 s compounds in the presence of carbon monoxide and hydrogen.

When they are used in the elemental form, it is advantager e ous to start with very finely dispersed metals in order to ensure that they are converted rapidly and completely into the catalytically active carbonyl complexes.

20 Cobalt compounds which can be added to the redaL- S* 44 tion mixture are salts such as cobalt 2-ethyhexanoate, *cobalt acetylacetonate, cobalt halides and cobalt nitrate, and also cobalt oxide or cobalt hydroxide. Cobalt carbonate has proved to be particularly suitable. Rulienium is likewise used in the form of the hotides, of the Oa 2-ethyhexanoate or of the acetylacetonate, and preferably in the form of the chloride RuCI 3

XH

2 0. BinucLear 4 ruthenium comptex compounds such as INH434 (Ru 2 0CL 10 dre also suitable. Of course, cobalt and ruthenium can also be employed as carbonyl compounds or derivatives thereof, such as C0 2

(CO)

6

L

2 (with L organic phosphane or phos phite) or RuX 2

(CO)

2

L

2 (with X halogen and L organic phosphane or phosphite).

Further cons uents of the catalysts are organic monophosphanes or bidentate organic phosphanes or phosphites of the general formula -Ar Ar a a A P (CH 2 O) a P (0) an a A a a Ar is here an aryl radical especially the ph nriyl radical, a is 0 or 1 and n is an integer from 1 to 6.

Examples of organic monophosphanes are the compounds tributylphosphane, trip lenylphosphane, tri-p-tolylphosphaine and trimethoxyphosphane. Examples of compounds according to the general formula, which can be used within the scope of the procedure according to the invention, are 1,2-bis(diphenylphosphino)methane, 1,3-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane and 1,4bis(diphenylphosphino)butane. 1,3-bis(diphenyLphosph ino)propane has proved to be particularly suitable.

Finally, the catalyst system also contains iodine 00 in a molecular or ionic form. Alkali metal iodides and, with particular advantage, cobalt iodide can be used as 15 salts of hydroiodic acid.

The catalyst system used in the process accordo Sing to the invention is normally added to the reaction 00 mixture in the form of its individual constituents. Although prior formation of the metal complex compounds, a 20 which are components of the catalyst system, is possible and in some cases advisable, it is not absolutely necessary. In order to avoid deactivation of the catalyst, c a~ exclusion of air must be ensured both during productiGo and during storage and use of the catalyst.

The catalyst system can be used repeatedly with- S, out deactivation, if the reaction products and the cyclic 'c C monoether or polyether are separated off with exclusion

S

4 t of air. If the catalyst system is used repeatedly, its activity even increases if 0.2 to 5% by weight, preferably 0.5 to 1% by weight of the cobalt originally used as Smetal or compound is added each time to the batches.

Methanol is normally used in the form of the product from industrial plants, with a water content of 4 to Additional purification is not necessary.

The reaction mixture originally employed contains S0.07 to 0.4 mol of water per mol of methanol. It has proved to be particularly advantageous to use 0.1 to 0.3 mol of water per mot of methanol. The addition of i ~water effects an increase in conversion. Larger quantities 1 00 G 0 e e o 0 e o 9 0i 0 O o oo 0 a 6 of water affect the conversion only to an insignificant extent, but smaller quantities lead to only insignificant increases in conversion or none at all. Advantageously, the water is fed together with the methanol to the reactor.

20 to 10,000, preferably 50 to 5,000 and especially 200 to 2,000 moL of methanol are employed per g atom of cobalt.

Cobalt and phosphane or phosphite are employed in a molar ratio from 1:0.1 to 1:20, preferably 1:0.1 to and especially 1:0.33 to 1:2.

The formation of propanol and butanol is favoured at the expense of the ethanol content in the reaction product by an increase in the Co/phosphane ratio. Thus, CoI 2 /phosphane in a molar ratio of 1:1 give only about 15 16% by weight of propanol and butanol, relative to the alcohols in the reaction product, whereas 66% by weight of propanol and butanol are obtained in a molar ratio of 3:1.

The cobalt/ruthenium atomic ratio is 1:0.0005 to 20 1:1, preferably 1:0.05 to 1:0.5 and especially 1:0.1 to 1:0.3.

The catalysts contain 0.002 to 3, preferably 0.1 to 2.5 and especially 0.5 to 2 mol of iodine per g atow of cobalt.

The carbon monoxide/hydrogen molar ratio in thu synthesis gas is usually about 1:2, but hydrogen can dt so be present in an excess over this ratio. Mixtures which contain CO and H 2 in the ratio of 1:3 to 1:4 can be used without disadvantages.

The carbon monoxide/hydrogen mixture should nut contain any impurities which affect the activity of thu catalyst system, such as sulphur compounds and hydrogen cyanide. Carbon dioxide and/or nitrogen up to 5% by volume, relative to the total mixture, are not harmful.

The novel process can be carried out either discontinously or continuously. In general, the reaction of methanol, carbon monoxide and hydrogen is carried out at temperatures from 180 to 250 0 C, preferably 180 to 230 0

C

and especially 200 to 220 0 C. The pressure is set to levels o ao 0 o

L

7 between 20 and 60 MPa, preferably 45 to 60 MPa and usLvcially 40 to 50 MPa. The methanol/synthesis gas molar ratio, that is to say the CH 3 0H/(CO+H 2 ratio, the CO/H 2 mixture being of the..composition indicated above, can be 1:0.1 to 1:20, preferably 1:0.5 to 1:5, in both the continuous reaction procedure and in the batchwise reaction procedure.

The residence time of the reactants in the reactor is up to about 8 hours, preferably 4 to 8 hours and es pecially 3 to 6 hours.

In the illustrative examples which follow, the invention is explained without restricting the scope thereof.

The experiments are carried out in autoclaves .o 15 which are fitted with gas inlet and outlet, thermocouple sensor, magnetic stirrer and heating jacket.

SThe autoclave is charged with the catalyst system 0* a o, and the methanol/water mixture at room temperature under air. The air is immediately displaced by repeated pres- S o 20 surizing with synthesis gas up to 2.0 MPa and careful Letting down. Synthesis gas is then injected up to a pressure of 5.0 MPa, the autoclave is heated up to the g oo desired reaction temperature and the desired reaction S *6 Spressure is set.

Unless otherwise stated, 0.2 mmol of Col2 0 0.04 mmol of RuI 2

(CO)

2 (PPh 3 2 S 0.2 imol of Nat 20 mmol of H 2 0 200 mmol of methanol are employed in the experiments (standard batch). The further reactants and the reaction conditions are to be found in the tabulated summaries in the examples. The synthesis gas contains two volumes of hydrogen per volutme of carbon monoxide.

After the predetermined reaction time has elapsed, the autoclave is cooled to 00C and slowly Let down to normal pressure. A sample of the cooled homogeneous reaction mixture is taken each time for analysis by gas chromotography.

8- The term seLectivity used in the evaLuatio ort the experiments is defined as follows: Si =moL MeOH converted to product i x 100 00o 0400 0 0 0 .0 0 0 00 0 0 000 000 0 00 0 o 0 0 0 0 0 0 00 0 0 g0 0 00 0 00 0 0 C 0 q 00 PPh 3

DPPM

OPPE

DPPP

DPPB

MeOH E t h0H P rO0H BuOH 15 SROH

SROH*

lISP 1R u 1 21 20 "RuCL 2 R u( a c ac) T H F mot- MeOlI converted in totaL In addition, the foLLowing abbreviations are tibed: t r ip Ien yipho sp han e 1,3 -b i s(d iph en yipIi osphin o )methane 1,3-bis(diphenyLphosphino)ethanL 1,3-bis (d iph en yipIi osph in o )prpane 1,3-bis(diphenyLphiosphino)butane met hano I e t hi an no L p ropano I but anoL total of the SEthoH S~O SBuOH setect ivities SEthOi SprOH S8u0H SAcetals higher boiling products Ru1 2

(CO)

2 (PPh 3 2 RuCL 2

(CO)

2 (PPh 3 2 3 Roithenium acety~acetonate tetrahydrofuran ExampLes 1 to 7 25 ExampLes 1 to 7 reproduce the state of the art.

They describe the reaction of methanol with synthesis (jas in the presence of cataLysts containing unidentate or hidentate phosphanes, but without an addition of dioxane to the reaction mixture. When triphenyiphosphane is used, the reaction products contain a very high propurtion of ethers and, when bidentate phosphanes are used, they still contain a significant proportion of ethers.

Tab Le 1 ExampLe No.~ 2 3 4 5 1 61 Temp. (00C 200 200 200 200 200 200 200 Pressure (MPa) 40 50 50 50 40 50 Phosphane PPh 3 PPh 3 DPPM DPPE DPPP DPPP DPPIJ Quantity (m mo L 0.2 0.2 0.2 0.2 0.2 0.2 Oc Time (hours) 3 3 3 3 3 3 *0 Products SeLectivity S~ M% 0 Ethers 23 23 13 9 12 12 18 Esters 10 11 13 15 10 8 -1 *00Acetats 0 0 9 11 7 3 6 a 00 00 0 000 HSP 0 0 2 5 0 3 60 EthOH 61 58 53 48 59 60 6 I PrOH+BuOH 6 8 10 12 10 14 9 00S RO*67 66 72 71 76 77 0 00 Conversion M% 77 83 81 87 85 91 _Mm~l~t~ 00 ooo ao 00 0 *0 0 0 0 oo 0 0 0 00 0 0 00 0 00 0 0 0 9 00 o 00 a o 9 00 0 00 0 00 0 00 o oo 0oo00 o o o 00 0 0 00 0 00 Examples 8 to 12 Examples 8 to 12 are carried out with the addi tion of varying quantities of dioxane. The formation of ethers decreases dras.tically, and the selectivity of the reaction with regard to the formation of alcohols is markedly increased.

Table 2 Example No. 8 9 10 11 12 Temp. (0C) 200 200 220 220 220 Pressure (MPa 50 50 50 50 550 Dioxane (mmoL: 100 100 100 200 300 DPPP (mmol) 0.2 0.2 0.2 0,2 0.2 Time (hours) 3 6 6 6 6 Products Selectivity S i Ethers 3 6 7 2 2 Esters 12 6 3 2 2 Acetals 23 3 1 0 2 HSP 0 4 0 0 0 EthGH 51 43 56 81 81 PrOH+BuOH 11 38 33 15 13 SROH* 85 84 90 96 96 Conversion 88 100 98 85 _I :i II: EXamptes 13 to 18 in Examples 13 to 18, the activity of different Ru, compounds is investigated. 200 mmoL of dioxane and 0.2 mmoL of DPPP areadded to the standard batch; the reaction takes place at 2200C and 50 MPa pressure;it is stopped after 6 hours.

The experiments show that the ruthenium compowirids do not substantially differ with respect to their activit Y a 0 a 9 0 a go Table 3 Example No. 13 14 15 16 17 16 Ru compounds "Rul 211 1 RUCL 2 RuCL 3 3H 2 0 RLJ(aCaC)., Products Selectivity S i M% Ethers 2 3 4 4 2 Esters 2 3 0.5 2 1 Acetals 0 2 1.5 2 0 H SP 0 0 0 0 0 0 EthOH 81 75 8 4 80 86 78 PrOH+BuOli 15 17 1 0 1 3 1 1 S RH96 92 94 93 97 Conversion 85 87 71 82 75 88 P 00 as O a6ca tu a a a c D oo j;-i 1

F

12 Examples 19 to 26 In ExampLes 19 to 26, the influence of the Cal 2 DPPP ratio on the pr6jiortion of the aLcohols in the reujction product is invest'igated. The reaction takes pLaci4 at 220 0 C and 50 MPa with the addition of 200 mmoL of dlioxane; it is stopped after 6 hours.

The SEth0Il/(SPrOH+SBu,0H) ratio can be Lowered from 5.4 down to 0.5 by increasing CoI 2 /DPPP from 1/1 to 3/1. At the same time, SPrOH/SBu OH is reduced from 8.8 to 3.7.

Table 4

I,

I'

I

Example No. 19 20 21 22 23 24 Col 2 (mmoL) 0.2 0.2 0.3 0.4 0.6 0.4 0.4 C].

DPPP CmmoL) 0.1 0.2 0.2 0.2 0.2 0.2 0.3 0.

Products Selectivity S. 4 a *1 I 4 0 4 0* so E th er s Esters Aceta Is Et hOH PrOH+BuOH S ROH S thOH (PrOH +SBuOH

IS

BuOH 2 2 0 81 96 5 .4 '17 3 3 26 3 43 43 86 4 .7 7.6 2.7 8 .7 0.8 4.9 0.8 1 .0 8.8 4.9 5.3 Conversion 13 ExampLes 27 to In ExampLes 28 and 30, THF is used as the cyclic ether, and its effectiveness is compared with that of dioxane (Examples 27'and 29).

Table Example No. 27 28 29 Temp. 0 C) 200 200 200 200 Pressure (MPa) 40 40 40 Phosphane DPPP DPPP DPPP DPPP Quantity (mmoL' 0.2 0.2 0.2 0.2 CycLic ether Dioxane THF Dioxane THF -Quantity (mmol, 100 100 100 100 Time (hours) 3 3 6 6 Products SeLectivity S. (%M Ethers 2.9 2.8 6.8 4.7 Esters 15.3 2.4* 3.2 AcetaLs 30.1 41.2 5.4 4.1 H SP 2.0 0 4. 5 4.8 EthOH 38.4 44.2 55.8 59.2 PrOH+BuOH 11.3 9.4 24.3 25.2 S ROH 49.7 53.6 80.1 84.4 Conversion M% 87.3 80.2 100 95.3 4 "C 4 44 4 C I 4 44 4 CC 44 4 4C I 41 II I 4414 44 4 1 II EthyL acetate not determined.

I 4 0 4 14 Under the reaction conditions applied, THF gives somewhat better selectivities with respect to SROIH but somewhat lower conversions than dioxane.

Examples 31 and 32 In Examples 31 and 32, the behaviour of the citalysts in repeated use with and without addition of CoI 2 is investigated. 0.2 mmol of DPPP and 200 mmol of dioxane are added to the standard batch. The reaction takes place at 220 0 C and 50 MPa pr.essure; it is stopped after 6 hours. The results of the individual experiments are compared in Table 6 with those of Example 11, Table 2.

b* a Table 6 0 0 0e 0 0 6 0* 0 00 00 0 0oe 0o O B0 a r* Example No. 11 31 32 Experiment 1 2 2 CoI 2 addition (mmol) 0 0 0 Products Selectivities S. Ethers 2 0 3 Esters 2 2 3 Acetals 0 20 7 EthOH 81 70 76 PrOH+BuOH 15 7 SRH 96 77 87 Conversion 85 55 73 'i j: i

I

.e a o 0 0 00 a 0 0 O0 0 0 0 0 00 o o 60 0 000 0 00 0 -1- I- -IOIS!k 1 1 15 Examples 11, 31 and 32 are carried out with the same catalyst system which is used for the first time in Example 11 kexperiment 1) and again in Examples 31 and 32 (experiment In Eyample 31, the catalyst is separated off in air, and in Example 32 it is separated off while air is excluded. For this purpose, the reaction so ut ion is taken from the autoclave under N 2 The reaction products and the dioxane are stripped off under an oil pump vacuum at 25 0 C. 20 mmol of water, 200 mmol of dioxane and 200 mmol of methanol are added under N 2 to the oily residue. The solution is then transferred into the autocldve, likewise under N 2 The examples show that the activity of the catdlyst system decreases in the course of the experiment.

The deactivation increases if air is not excluded during the separation of the catalyst and the re-use (Example 31).

Examples 33 to Table 7 Example No. 11 33 34 Experiment 1 2 3 4 Col 2 addition (mmol) 0 0.1 0.1 0 Products Selectivities S. Ethers 2 0 4 4 Esters 2 1 4 2 Acetals 0 2 4 0 EthOH 81 71 60 73 PrOH+BuOH 15 26 28 21 SROH 96 97 88 94 Conversion 85 94 97 94 0 00 0 0 00 0 00 0 C0 0 00 a o 0 00 00 o 0 00 0 0 0 0 0 16 The separation of the catalyst system from the reaction product and dioxane and its re-use in the synthesis are carried out as in Example 32. Overall, the same catalyst is used.four times, and Co 12 is added in each of experiments 2 and 3 (Examples 33 and 34) in order to overcome the deactivation. Compared with experiment 1 (Example 11), the conversion is increased and SROH is kept approximately constant by the addition of Col 2 (Table o C o 0 a L 08oe 0o 0 a e I 0 g s 0 00 0 8O 9 e

Claims

8. 1. Process for producing ethanoL in a mixture with cLa propanol and butanol by reacting methanol with carbon to monoxide and hydroget at temperatures from 180 to 250 0 C use and pressures from 20 to 60 MPa in the presence of 0.07
9. to 0.4 mol of water per mot of methanol and of catalysts ciai which contain cobalt and ruthenium in the elemental form phos or in the form of compounds, iodine or iodide and an org- pref anic monophosphane or phosphite or a bidentate organic phosphane or phosphite, character.ized in that 0.2 to cAAc110 clai 4 mot of a cyclic monoether or poLyether per moL of methanol are added to the reaction mixture. 0* espe 2. Process according to Claim 1, characterized in g
11. that 0.3 to 3 mot and especially 0.5 to 1.5 mot of a cy- c .1 clain 0 clic monoether or polyether per mol of methanol are o .to 3, 0 *added. 0 0 oa 00 0 odi a 00 3. Process according to CLaim 1 or 2, characterized
12. in that the cyclic monoether or polyether is tetrahydro- cam Sso claim furan or dioxane. 0 m 00 molar 4. Process according to one or more of the preceding a 0 13. 0 0 0* claims, characterized in that organic bidentate phos- 0 a cLaim Sphanes or phosphites of the general formula 0 use on Ar aa A P (CHl P Aof th Ar n a Ar-()a Aaa 00 added a0 0 0 o in which Ar is an aryl radical, especially the phenyl 60oo00 00 o ated radical, a is 0 or 1 and n is an integer from 1 to 6, Q 1
14. are used as a constituent of the catalysts. cLaima- Process according to Claim characterized in at ten that tributylphosphane, triphenytphosphane, tri-p-totyL- and es phosphane or trimethoxyphosphane are used as the organic 60 MPa monophosphane. MPa. 6. Process according to Claim 4, characterized in that 1,2-bis(diphenyLphosphino)methanrie, 1,3-bis(diphenyL- phosphino)ethane, 1,3-bis(diphenylphosphino)propane or 1,4-bis(diphenylphosphino)butane are used as organic bi- dentate phosphanes. 7. Process according to one or more of the pre- A ceding claims, characterized in that the reaction mix- U 9 ture contains 0.07 to 0.4 and e';peciaLLy 0.1 to 0.3 mot o 2 of water per moL of methanol. 8. Process according to one or more of the preceding claims, characterized in that 20 to 10,000, preferably to 5,000 and especially 200 to 2,000 mol of methanol are used per g atom of cobalt. 9. Process according to one or more of the preceding claims, characterized in that cobalt and phosphane or phosphite are used in a molar ratio from 1:0.1 to 1:20, preferably 1:0.1 to 1:5 and especially 1:0.33 to 1:2. Process according to one or more of the preceding claims, characterized in that the cobalt/ruthenium atomic S, ratio is 1:0.0005 to 1:1, preferably 1:0.05 to 1:0.5 and especially 1:0.1 to 1:0.3. e 11. Process according to one or more of the preceding Ok 8claims, characterized in that the catalysts contain 0.002 to 3, preferably 0.1 to 2.5 and especially 0.5 to 2 mol of o0 0 °ot iodine per g atom of cobalt. 12. Process according to one or more of the precedging o claims, characterized in that the methanol/synthesis gas 0 molar ratio is 1:0.1 to 1:20, preferably 1:0.5 to 0 00 o0 0 13. Process according to one or more of the preceding o a claims, characterized in that, in the case of repeated 0 a use, 0.2 to 5% by weight, preferably 0.5 to 1% by weight, of the cobalt originally used as metal or compound are aoo added each time to the catalyst, after it has been separ- 0 00 00o ated from the reaction product. 0 0 0 O 0 14. Process according to one or more of the preceding claims, characterized in that the reaction is carried out at temperatures from 180 to 2500C, preferably 180 to 2300C and especially 200 to 2200C and under pressures from 20 to MPa, preferably 45 to 60 MPa and especially 40 to MPa. DATED this 25th day of August 1988. HOECHST AKTIENGESELLSCHAFT EDWD. WATERS SONS PATENT ATTORNEYS QUEEN STREET MELBOURNE. VIC. 3000.