DD280752A1 - METHOD FOR THE CATALYTIC MANUFACTURE OF AN ALCOHOL MIXTURE WITH INCREASED ISOBUTANOL CONTENT - Google Patents

Abstract

The invention relates to a process for the catalytic preparation of an alcohol mixture having an increased proportion of isobutanol by reacting CO and H2 over base-modified zirconium / zinc / manganese catalysts. The alcohol mixture prepared according to the invention is used as an octane improver in fuels.

Description

Field of application of the invention

The present invention relates to a process for preparing a Alkoho''gernischs with an increased proportion of isobutanol by reacting CO and H ₂ over base-modified zirconium / zinc / manganese catalysts.

The alcohol mixture is suitable as Oktanzahlverbesserer for gasoline fuels and as a raw material for the production of methyl tert, butyl ether.

Characteristic of the known state of the art

The synthesis of isobutanol-containing alcohol mixtures has long been known. Under the name isobutyl oil synthesis, a process for the recovery of isobutanol from synthesis gas by BASF from 1935-52 was carried out on a large scale.

Kaliumalkalisierte high-pressure ZnG-C ^ Oa-methanol contacts were used (szBA Palm in Chem. Technology III Organic Technology I, K. Winnacker, L. Küchler, Carl Hauser Verlag, Munich, p 359 et seq. (1971) and pp. 572 ff. [1981] The large-scale yields of 11-14% i-BuOH in the liquid product were achieved by using ZrO ₂ systems with those containing gallium, aluminum, chromium and, above all, indium oxide with alkali metals are offset to 20-40% i-BuOH in the liquid product (see DE-OS 928045) .This principle takes up the Snamprogetti SpA in their patents DE-OS 3214313, DE-OS 3136088, DE-OS 3119290 and FR 2490215auf and achieves 23.2% i-BuOH in the liquid phase according to a specific production process with Zn-Cr ₂ O 3 -K ₂ O catalysts.

By means of alkali-modified low-pressure methanol contacts CuO-ZnO-K ₂ O, Südchemie AG achieves 11.3% butanols in patent DE-OS 3005511. Standard Oil Co. EP-A-0005492, US 4533775 and US 4559316 describe rare earth rare earth Cu-Zr-Mn-alkali catalysts.

The Institut Francais du Petrole uses in the published patent applications DE-OS 2949952, DE-OS 3310540, DE-OS 3616519, DE-OS 3516928, FR 2543945 and FR 2504916 CuOZnO-CoO-alkali contacts, which with Pd, rare earth , Na and Li promoters.

The Octamix procedure of the company Lurgi uses alkalized low pressure methanol contacts and achieves max. 6-7% butanols

(see Petroleum and coal, natural gas, petrochemistry, 38, 19-22 [1985] and DE-OS 3403492).

The BP Co. receives in EP 100607 with a CuO-CoO-alkali contact with Ag, Ga, Zr, Zn, Th and Pr, Pt or Ni as a promoter at 19% CO conversion yields of butanols of 7%.

Kotowski achieves with the CuO-ZnO-Mn ₂ O ₃ contacts 10.9% butanols in the liquid phase (see Chem.Sosow; 28 [1], 169-77 [1984]).

Even Klier receives at comparatively mild reaction conditions (p = 7.5 MPa, T = 560-600K) 15% i-BuOH at selectivities of 6% by means of CuO-ZnO-Cs ₂ O catalysts (see Preprints Papers, Am.Chem. Soc, Div., Fuel Chem., 29 (5) 173-80 [1984].

A synthetic zeolite and thus completely different catalyst systems describes DD-OS 219397 of the VEB-Leuna-Werke.

The carrier is charged with CuO, CoO, Cr ₂ O ₃ or FeO or Mn ₁ Oy and contains K ₂ O as the basic component. Selectivities of up to 6.3% n-BuOH are achieved. Goudeau also reports in Cimm.Eur. Communities, Eur (1985) Eur 10024, Energy Biomass, 959-62 (FR). Alumosilicates of the 13-X type or mordenite type which are impregnated with copper, zinc, thorium and cerium. At 523-673 K and 5 MPa, it achieves levels of 40% i-BuOH in the liquid phase at about 20% CO conversion. Unfortunately, liquid products such as water are excluded from the balance so that no direct comparability with other catalyst systems is possible.

In DE-OS 35 24317 is a process for the preparation of an alcohol mixture with increased Isobutanolgehal! in which catalysts are used which contain ZrO ₂ and / or Ce ₂ O ₃ , Pd and a base. In addition, elements of the group B, Al, Ga ₁ In, Ti, Si, Ge, Sn, Pb, Cu, Zn, Sc, Y, La, Ti, Hf, Th, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt and rare earths except for cerium.

In the same document, another catalyst is disclosed which contains ZrO ₂ and / or Ce ₂ O ₃ and manganese and a base.

In Table 2 of this document catalysts are disclosed which contain ZrO ₂ , Ce ₂ O ₃ , K ₂ O, MnO and Pd.

Table 5 discloses catalysts which additionally contain In ₂ O ₃ , Fe ₂ O ₃ , CuO, Dr ₂ O ₃ , Al ₂ O ₃ and La ₂ O ₃ .

Finally, Table 7 contains catalysts without MnO, which contain ZrO ₂ , K ₂ O, Pd and the metal oxides ThO ₂ , CuO, ZnO, MgO and Cr ₂ O ₃ .

The highest isobutanol content of 43.6 uew .-% at a space / time yield (g / lh) of 392 is obtained with a catalyst of ZrO ₂ , K ₂ O, MnO and Pd (K4, Tab.3). With the same catalyst under changed process conditions, a space / time yield of 1059 and an isobutanol content of 30.2 wt .-%.

Object of the invention

The invention provides a process, improved over the prior art, for producing an alcohol mixture having an increased isobutanol content. With the catalyst system according to the invention, the selectivities with respect to isobutanol can be considerably increased with satisfactory to very good space-time yields.

 3- 2JI0 752

Presentation of the weaving of the invention

It is an object of the present invention to develop an improved process for the preparation of an alcohol mixture having an increased isobutanol content from synthesis gas using a novel catalyst system.

The Applicant has now surprisingly found that compared to the prior art even better and sometimes much better results are obtained.

According to the invention, these results are obtained by a process for preparing an alcohol mixture having increased isobutanol content from CO and H ₂ or CO ₂ and H ₂ or mixtures of CO ₂ and CO and H ₂ or other CO and / or CO ₂ and H ₂ -containing gases, characterized in that the preparation is carried out in the presence of a catalyst which comprises the following components:

a, 5-80% by weight of zirconium in elemental form and / or in the form of its compounds,

b, 5-80Gθw ·% Zn in elemental form and / or in the form of its compounds, O ₁ 1-80% by weight Mn in elemental form and / or in the form of its compounds,

d, 0.0001-10% by weight of a basic and / or basic compound convertible from the group of the alkali and / or alkaline earth metals and / or ammonia and / or the basic and / or basic compounds of the invention ammonia.

Very good results are also obtained if in addition Pd is contained in elemental form or in the form of si.'iner compounds in the catalyst.

Although in the prior art catalysts with numerous combinations of elements or their compounds.

in particular their oxides are described, the inventive combination Zr-Zn-Mn is mentioned at no point. Eb was unpredictable and surprising to those skilled in the art that it is precisely this combination in the presence of bases that gives superior results.

It is known that high isobutanol-containing alcohols are very useful as octane enhancers in fuels because, unlike methanol and ethanol, they are not prone to phase separation even in the presence of moisture or smaller amounts of water.

The catalyst used in the process according to the invention may contain 5-80% by weight of zirconium, preferably 20-80% by weight. The zircon may basically be present in elemental form and / or in the form of its compounds, but preference is given to catalysts which contain zirconium oxide ZrO ₂ or else zirconates. It may also be mixtures of these components mentioned.

Zinc may also be included in the catalyst in an amount of 5-80% by weight, and preferably 2O-80% by weight.

The zinc kai; .ι basically be contained in elemental form and / or in the form of its compounds. ZnO is preferred, but also zinc oxide hydrates or zincates are particularly suitable. It may also be mixtures of these components mentioned.

Manganese may be present in the catalyst at 1-80% by weight, and preferably at 10-80% by weight, both in elemental form and in the form of its compounds. Preferred compounds are, in particular, manganese oxides, manganese hydroxides, manganese oxide hydrates and manganates.

It may also be mixtures of these components mentioned.

Suitable basic components in the catalyst are the basic compounds of alkalis and / or alkaline earths, in particular the oxides and hydroxides, but also other basic compounds, e.g. Carbonates, bicarbonates, amides and the like are suitable for the purposes of the invention, but also ammonia and amines and / or basic compounds of ammonia and amines. The basic component, which may also consist of mixtures of the abovementioned compounds, is present in an amount of from 0.0001 to 10% by weight, preferably from 0.001 to 5% by weight and more preferably from 0.05 to 5% by weight. contained in the catalyst.

Also compounds of alkalis, alkaline earths, NH ₃ and amines which form basic compounds can be used according to the invention, such as. As metal hydrides + H ₂ O or ammonium compounds that form ammonium hydroxide by hydrolysis.

In the case of adding palladium, the catalyst contains palladium in an amount of 0.001-10 wt%, preferably 0.01-2 wt%.

Although the palladium in the ready-to-use catalyst is generally in elemental form, it may also be present in the form of compounds, even in a mixture of elemental and bound forms.

Other elements in particular of the 1st, 2nd, 3rd and 8th subgroup of the periodic table can be contained in the same form and amount as a single component, in admixture with Pd or in other mixtures with one another in the catalyst. Examples are Au, Ag, Cu, Sc, Y, lanthanides, Ru, Rh, Os, Ir and Pt. It is crucial that the combination a-d claimed in claim 1 is contained in the catalyst.

In the process of the invention, the reaction with CO and H ₂ or CO ₂ and H ₂ or mixtures of CO ₂ and CO with H ₂ or other CO and / or CO ₂ and H ₂ gases contained in the presence of the catalysts of the invention in a Temperature of 420-825K, preferably from 570-760K and more preferably from 600-730K instead, at a pressure of 10-480 bar, preferably from 20-400 bar and particularly preferably at 50-380 bar and a GHSV (gas hourly space velocity) of 1000-10000Oh "', preferably 2000-7500Oh" ¹ and more preferably 5000-40000h ~' instead.

A's feed gas may be conventional synthesis gas containing predominantly CO and H ₂ , but CO ₂ and other gases such as H ₂ O vapor, N ₂ , CH ₄ and others may also be included. As is known, for stoichiometric reasons, the proportion of higher alcohols in the product increases at a relatively high CO content. A suitable gas mixture contains, for example, CO: H ₂ in a ratio of 1: 1. However, the ratio can vary within wide limits from about 1:10 to 10: 1.

According to the stoichiometry

4 CO + 8 H ₂ - C ₄ H ₉ OH + 3 H ₂ O or: 7 CO + 5 H ₂ 1; C ₄ H ₅ OH + 3 CO ₂

and the coupling of by-products CO ₂ and H ₂ O via the water gas shift equilibrium CO + H ₂ O CO ₂ + H ₂

Optionally, by selecting the CO / H ₂ ratio, the reaction can be selectively directed to the desired product composition. At high hydrogen levels, up to 30% water is obtained in the reaction product and high proportions of lower alcohols, especially methane. At high CO contents in the feed gas, the selectivity to i-BuOH increases. There is little water in the reaction product and much converted CO ₂ . With CO / H ₂ ratios> 3/1, the proportion of higher alcohols and the proportion of ketones in the reaction product increases. Total space-time yields decrease with increasing CO content in the feed gas. In addition to COZH ₂ , the addition of alcohols such as C, -C ₀ -Alkohoien, in particular of methanol, to the feed gases has been found to be positive for the selectivity to i-BuOH. The addition of n-propanol and methanol in a reducing atmosphere also increases the yield of i-BuOH. In addition to synthesis gas, the methanol can also be supplied in anceren, preferably ι eduzierenden carrier gases to the catalyst under reaction conditions, but also without dilution in gases methanol can be fed directly to the catalyst. The advantage of using methanol in the feed gas is the lower positive heat of reaction.

The representation of the catalysts is z. B. by coprecipitation or successive Precipitation represents corresponding metal salt solutions, preferably their nitrates. The precipitation of the catalysts but also know by complexing agents, such as hydroxy, poly, amino acids or amino alcohols done.

Precipitation of the catalysts is carried out under temperature and pH control. The preparation is carried out at 290-400K, preferably at 330-373K and pH values of pH 3-13, preferably pH 7-11. In this case, the pH can be varied by the addition of metal salt or base solution during the precipitation, but is preferably kept constant to produce homogeneous basic body. The concentration of the metal salt and base solution can be varied within wide limits, but is preferably carried out in the range of 0.1-5 mmol " ^1. The catalyst may be preferred after precipitation at temperatures of 290-500 K, 0-50 hours The hydrated base contact thus obtained can optionally be washed and aged again After shaping into cylindrical pellets, the contact is dried at temperatures of 330-430 K and heated thermally at temperatures of 420-875K, preferably 50O-700K in Over a period of 1 to 10 hours, and can then be reduced with hydrogen at elevated pressure (2-250 bar) and elevated temperature (400-700 H.) The shaping can be carried out by means of extruders or by pressing or other means During drying, calcination and reduction, the weight of the hydrated precipitate is generally about 10-15% of the original catalyst reduced (TGA). The impregnation with components from the subgroups of the Periodic Table takes place before or after the calcination. The noble metals are generally enriched as soluble compounds (eg, nitrates) in water or as organic compounds (eg, acetylacetonates or complexes such as carbonyl complexes) in organic solvents (eg, alcohols or acetonitrile). In this case, for example, the incipient wetness method, a slow impregnation or other suitable methods can be used. The noble metals may be incorporated into the contact by co-precipitation or successive precipitation, but surface impregnation is preferred. The organic or inorganic radicals of the noble metal can be thermally destroyed by calcination. If carriers are used, activation by calcination can also be carried out after application of the desired components by impregnation. Furthermore, a binder (such as graphite, stearic acid and their esters, cellulose or other vegetable materials) can be added to the precipitation mixture, whereby a specific pore size can be produced by targeted decomposition or by separation. The noble metal coated catalysts are optionally used directly in the reaction, but preferably again dried, calcined and reduced. The reduction takes place in reducing gases, preferably hydrogen with vol. Portions of 0.1-100%, preferably 50-100% at Drückon of 2-250 bar, preferably 10-100 bar with Volumengeschv. ^{! r>} r) CANDIES of 500-10000Oh ^"1, preferably from 5,000 to 20,000"'. The described production methods are exemplary, but not limiting. Other preparation methods are suitable for the preparation of the catalysts of the invention.

Ausführungsbeisplelo

With the aid of the following exemplary embodiments in the form of experiments summarized in tables, the present invention will be explained in more detail.

Unless otherwise stated, the reaction was carried out with a CO / H ₂ ratio of 1: 1.

In the tables, the data are comparable to those of the prior art according to DE-OS 3524317. This application was filed by the same Applicant as the present invention.

In Table 1, the ratio ZrO ₂ : ZnO: Mn »O _{y is} varied. Pressure, temperature and precipitation pH are the same. The bases used are KOH, LiOH and NH ₃ .

The experiments show that a ratio of 1: 1: 1 (based on molar amounts of the nitrates used) leads both to a good space-time Ausb6ute, as well as to a comparatively high Isobutanolseletaivität, which is 44Gew .-% higher than the best attempt of DE -OS 3524317 from Table 3 with 43.6 weight% and a space-time yield of 392g / l. H.

Table 1

Dependence of the space-time yield and isobutanol selectivity on the ratio ZrO ₂ : ZnO: Mn _x Oy with K ₂ O, Li ₂ O and NH ₃ nls base

catalyst WF 77 WF 85 WF 79 WF 93 WF162 WF163 WF164 Mark Ratio * 1: 1: 1 2: 2: 1 2: 1: 2 2: 2: 1 1: 4: 3 1: 6: 1 5: 1: 1 ZrO ₂ -ZnO-Mn _x Oy reaction 700 700 700 688 700 700 700 temperature, K reaction 250 250 250 250 250 250 250 pressure, bar GHSV / h ' ¹ 20000 20000 20000 20000 20000 20000 20000 Space-time yield 920 810 715 280 320 370 1005 g / l h (alcohols) Isobutanol Selek 44 40 39 43 27 28 41 Activity, wt.% Precipitation pH 9 9 9 9 9 9 9 base K ₂ O K ₂ O Li ₂ O NH ₃ K ₂ O K ₂ O K ₂ O

* based on salted molar amounts of metal compounds

Table 2 shows the influence of the reaction temperature. The catalyst used was ZrO ₂ -ZnO-Mn _x Oy-K ₂ O in the ratio 1: 1: 1. The precipitation pH was 10.

The table shows that the space-time yield at about 675K goes through a maximum of 850g / lh, but the isobutanol selectivity increases to 55wt% at 700-71uK and drops again at even higher temperature.

Table 2

Influence of the reaction temperature on space-time yield and isobutanol solubility

Catalyst- 600 625 WF115 675 700 715 725 kennzeichsn Ratio * 1: 1: 1 250 ZrO ₂ -ZnO-Mn _x Oy reaction 650 20000 temperature K 550 685 850 855 710 625 reaction pressure, bar 3 18 45 55 55 52 GHSV / h " ' Space-time yield 725 11 g / l h (alcohols) K ₂ O Isobutanol Selek 29 Activity,% by weight Precipitation pH base

* based on used) molar amounts of metal compounds

With the same catalyst, the influence of the pressure was examined according to Table 3. While the space-time yield increases up to about 3C0 bar to 805 (l / h, the isobutanol selectivity drops from 58% by weight to 38% by weight at 350 bar.

Table 3

Influence of reaction pressure on space-time yield and isobutanol selectivity

catalyst 50 100 - WF115 250 300 350 Mark Ratio * 1: 1: 1 20000 ZrO ₂ -ZnO-Mn _x Oy 240 445 755 805 765 reaction 700 temperature K 58 58 150 55 48 38 reaction pressure, bar 11 GHSV / h " ¹ 565 K ₂ O Space-time yield g / l h (alcohols) 55 Isobutanol selectivity tivity, wt .-% Precipitation pH base

* based on molar amounts of metal compounds used

Table 4 relates to the influence of the gas load when using the same catalyst. The maximum of the space-time yield is at a GHSvVh " ¹ of 20000-25000, while the maximum isobutanol selectivity of 61 wt .-% at a GHSVVh" ^{1 is} about 10000.

Table 4

Influence of gas load on space-time yield and isobutanol selectivity

catalyst 5000 10000 WF115 25000 30000 Mark 545 680 760 660 Ratio * 1: 1: 1 ZrO ₂ -ZnO-Mn _x Oy 59 61 50 36 reaction 700 temperature K reaction 250 pressure, bar GHSV / h " ¹ 15000 20000 Space-time yield 710 755 g / l h (alcohols) Isobutanol selectivity 56 55 Activity,% by weight Precipitation pH 11 base K ₂ O

• Based on used Moimengen on metal compounds

Table 5 shows the influence of the base used. It is clear that at the same precipitation pH of 9, K ₂ O and Cs ₂ O have a favorable effect on the space-time yields, while Na ₂ O leads to the highest Isobutanolselektivität of 62Gew .-% under the conditions indicated. Accordingly, even better results should be obtained with mixed bases.

Table 5

Dependence of space-time yield and isobutanol selectivity on the base used

catalyst WF 77 WF 89 WF 95 WF 97 WF101 WF103 Mark Ratio * 1: 1: 1 1: 1: 1 1: 1: 1 1: 1: 1 1: 1: 1 1: 1: 1 ZrO ₂ -ZnO-M n, O _y reaction 700 700 700 700 700 700 temperature K Rsaktions- 250 250 250 250 250 250 pressure, bar GHSV / h " ¹ 20000 20000 20000 20000 20000 20000 Space-time yield 810 680 850 510 355 465 g / l h (alcohols) Isobutanol selectivity 44 62 50 40 35 60 civility,% by weight Fällunys pH 9 9 9 9 9 9 base K ₂ O Na ₂ O Cs ₂ O MgO SrO BaO

* based on molar amounts of metal compounds used

Tables 6 and 7 show the influence of the precipitation pH when using K ₂ O and Li ₂ O as bases. It can be seen that in the case of K ₂ O, a precipitation pH of 7 or 11 is particularly beneficial for space-time yield and isobutanol selectivity, with over 50 wt% i-butanol in the liquid phase, while with Li ₂ O as base Maximum of the space-time yield is about 835 g / lh and a pH 8, while in agreement with K ₂ O as the base, the Isobutanolselektivität with increasing precipitation pH increases up to 64Gew .-%.

Table β

Influence of precipitation pH on space-time yield and isobutanol selectivity with K ₂ O as base

catalyst WF105 WF107 WF109 WF111 WF 77 WF113 WF115 WF117 Mark Proportion · 1: 1: 1 1: 1: 1 1: 1: 1 1: 1: 1 1: 1: 1 1: 1: 1 1: 1: 1 1: 1: 1 ZrO ₂ -ZnO-Mn, O _y reaction 700 700 700 700 700 700 700 700 temperature K reaction 250 250 250 250 250 250 250 250 pressure, bar GHSV / h " ' 20000 20000 20000 20000 20000 20000 20000 20000 Raumzeitäusbeute 165 240 380 895 920 1045 905 240 g / l h (alcohols) Isobutanol selectivity 21 39 58 42 44 46 51 27 tivity, wt .-% Precipitation pH 3 5 7 8th 9 10 11 13 base K ₂ O K ₂ O K ₂ O K ₂ O K ₃ O K ₂ O K ₂ O K ₂ O

• based on molar amounts of metal compounds used

Table 7

Influence of precipitation pH on space-time yield and isobutanol selectivity with Li ₂ O as base

catalyst WF142 WF144 WF146 WF148 Mark Proportion · 1: 1: 1 1: 1: 1 1: 1: 1 1: 1: 1 ZrO ₂ -ZnO-Mn _x Oy reaction 715 715 715 715 temperature K reaction 250 250 250 250 pressure, bar GHSV / ir ¹ 20000 20000 20000 20000 Space-time yield 550 835 755 440 g / l h (alcohols) Isobutanol selectivity 18 49 53 64 tivitet, wt .-% Precipitation pH 6 8th 10 11 base Li ₂ O Li ₂ O Li ₂ O Li ₂ O

* based on molar amounts of metal compounds used

In the experiments summarized in Table 8, a catalyst was used consisting of ZrO ₂ -ZnO-MnO in the ratio 1: 1: 1. The precipitation pH with K ₂ O as base was 9.

In addition, elements from the 1st, 2nd and 8th subgroups were added to the catalyst. By far the most favorable Pd, compared to Au, Pt, Ru and Cd.

Table 8

ZrO ₂ -ZnO-Mn _x Oy 1: 1: 1 "

Influence of an additional element from the 1st, 2nd and 8th subgroups on the space-time yield and isobutanol selectivity Precipitation pH 9, base: K ₂ O.

catalyst WF104 WF119 WF122 WF114 WF 67 Mark additional element Pd Au Pt Ru Cu ·· (0.25% by weight) reaction 700 700 700 700 700 temperature K reaction 250 250 250 250 850 pressure, bar GHSV / h ' 20000 20000 20000 20000 20000 Spacetime-off 810 595 245 225 610 prey g / l · h Isobutanol selectivity 54.0 47.6 34.0 22.2 44.3 tivity, wt .-%

¹ 1: 1: 1 based on moles of metal compounds used

In the following experiments, the combination ZrO ₂ -ZnO-Mn _x Oy-Pd was investigated in more detail. Table 9 shows the gas load and its effect on space-time yield and isobutanol selectivity. A 0.25 wt% Pd catalyst with a ZrO ₂ / ZnO / Mn "Oy ratio of 1: 1: 1 * was used. The base used was K ₂ O. The vial shows that the maximum of the space-time yield at a GHSV / h " ^{1 is} from 20,000 to 2,000, namely from 1010 to 1, 2 μ / lh The isobutanol selectivity is at GHSV / h "'from 5000 to 15000 constant at about 62% by weight and then drops to 5a, 4% by weight at a GHSV / h"' of 25,000.

Table 9

Influence of the gas load on the space-time yield and the isobutanol selectivity with the catalyst: ZrO ₂ -ZnO-Mn _x O y 1: 1: 1, 0.25 wt% Pd, base: K ₂ O.

catalyst WF116 WF116 WF116 WF116 WF116 WF11I Mark Temperature K 715 715 715 715 715 715 printable 250 250 250 250 250 250 GHSV / rT ¹ 5000 10000 15000 20000 25000 30000 Fällur.gs pH 10 10 10 10 10 10 Spacetime-off 685 935 990 1010 1095 915 prey g / l h Isobutanol selectivity 62.5 62.0 62.7 61.1 59.4 29.1 tivity, wt .-%

* based on moles of metal compounds used

Table 10 shows the influence of the precipitation pH for the same catalyst composition. Here, the Boreich of pH 9-10 is particularly favorable in terms of Raumzeitausbetjte and Isobutanolselektivität.

Table 10

Influence of the precipitation pH on space-time yield and isobutanol selectivity with the catalyst: ZrO ₂ -ZnO-Mn _x O y 1: 1: 1, based on moles of metal compounds used, 0.25 wt.% Pd, base: K ₂ O.

Catalyst WF106 WF108 WF110 WF112 WF114 WF116 WF118 WF156

Label TempuraturK Printable GHSV / ir 'Precipitation-pH Space-time yield g / l h

Isobutanol 20.7 48.3 63.4 37.3 54.0 51.5 12.5

Selekt. G "w .-%

Finally, Table 11 shows the influence of the amount of Pd in the catalyst. Cheap Pd amounts are 0.15-0.25 wt .-%.

Table 11

Influence of the added amount of Pd on the space-time yield and the Isobutanolselektivität with the catalyst ZrO ₂ -ZnO-Mn _x 0y1: 1: 1 *, base: Li ₂ O.

700 700 700 700 700 700 700 700 250 250 250 250 250 250 250 250 20000 20000 20000 20000 20000 20000 20000 20000 3 5 7 8th 9 10 13 without base 160 379 515 830 810 950 250 2

catalyst WF150 WF151 WF 149 WF152 WF15 Mark Temperature K 700 700 700 700 700 printable 250 250 250 250 250 GHSV / h " ' 20000 20000 20000 20000 20000 added amount 0.05 0.15 0.25 0.5 1.0 on Pd in% Precipitation pH 11 11 11 11 11 Space-time training 500 700 735 510 530 bouteg / l · h Isobutanol Selek 47.0 46.9 41.3 17.9 18.6 Activity,% by weight

* based on molar amounts of metal compounds used

The variation cos CO / H ₂ ratio 6S is given in Table 12. A ZrO ₂ -ZnO-Mn _x O _y -Pd catalyst was used (0.25 wt.% Pd, precipitation pH 9).

The best result in terms of space-timeout and isobutanol selectivity was achieved with a CO / H ₂ ratio of 1: 2.

As the CO / H ₂ ratio increases, the space-time yield decreases sharply, while the isobutanol selectivity increases somewhat.

Table 12 1: 2 CO / H 700 Temperature" 25 Pressure, bar 20000 GHSV / h " ¹ 635 Spacetime-off prey g / l · h 50.8 Isobutanol selectivity tivity, wt .-%

700

25

20000

475

47.7

-10- 280 752 2: 1 3: 1 700 700 25 25 20000 20000 450 240

54.2

54.2

Table 13 shows that can be greatly influenced by the addition of methanol vapor space-time yield and selectivity to isobutyl alcohol, (same catalyst).

Table 13

CO / H ₂ (1: 1): MeOH 1: 0 3: 1 2: 1 1: 1 Temperature «pressure, bar GHSV / h- ' 700 10 20000 700 10 15000 700 10 13 500 700 10 10000 Space-time yield 295 700 1690 3960 lsobut.-Selek.Gev.-7o 30.9 38.1 45.2 57.2

Good results can also be achieved if the catalysts of the invention on supports in particular

neutral or basic metal oxides.

Furthermore, good results are also obtained with CO ₂ / H _? u id CO / CO ₂ / H ₂ gas mixtures.

The results according to the invention show that the selectivities with respect to isobutanol can be significantly increased with the claimed catalyst system with satisfactory to very good space-time yields.

Claims (20)

1. A method for katalyti .. Chen production of an alcohol mixture with increased iscbutanolgehalt of CO and H ₂ or CO ₂ and H ₂ or mixtures of CO ₂ and CO and H ₂ or other CO and / or CO ₂ and H ₂ contained gases, characterized in that the preparation of the alcohol mixture is carried out in the presence of a catalyst which comprises the following components: a, & -80% by weight of zirconium in elemental form and / or in the form of its compounds, b, 5-80% by weight of Zn in elemental form and / or in the form of its compounds, c, 1-SO% by weight of Mn in elemental form and / or in the form of its compounds, d, 0.0001-10% by weight of at least one basic and / or basic compound-convertible compound from the group of the alkali and / or alkaline-earth metals and / or ammonia and / or the basic and / or basic compound Compounds of ammonia. 2. The method according to claim 1, characterized in that it is carried out in the presence of a catalyst which preferably contains 20-80 wt .-% zirconium. 3. Process according to claims 1 and 2, characterized in that it is carried out in the presence of a catalyst which preferably contains 20-80 wt .-% Zn. 4. Process according to claims 1-3, characterized in that the reaction is carried out in the presence of a catalyst which preferably contains 10-80% by weight of manganese. 5. Process according to claims 1-4, characterized in that it is carried out in the presence of a catalyst which preferably contains 0.001-5 wt .-% of component d. 6. Process according to claims 1-5, characterized in that it is carried out in the presence of a catalyst which additionally contains at least one element from the groups 1, 2, 3 and 8 subgroup of the periodic table in an amount of 0.001 to 10Gew .-%, preferably from 0.01 to 2 wt .-% in elemental form and / or in the form of its compounds. 7. Process according to claims 1-5, characterized in that it is carried out in the presence of a Kc'alysators, which additionally 0.001 to 10Gew .-%, preferably 0.01-2Gew .-% Pe liadium in elemental form and / or in Contains form of its connections. 8. Ve / drive according to claims 1-7, characterized in that it is carried out in the presence of a catalyst which contains the components zirconium, zinc and manganese in the form of oxides. 9. Process according to claims 1-8, characterized in that at a temperature of 420-825 K, preferably from 570-760 Kund particularly from 680-730 K, at a pressure of 10 to 480 bar, preferably from 20 to 400 bar and more preferably from 50 to 380 bar and a GHSV (gas hourly space velocity) of 1000-100000 h " ¹ , preferably from 2000-7500Oh" ¹ and more preferably from 5000-4000Oh " ^{1 is} working. 10. The method according to claims 1-9, characterized in that a CO / H ₂ mixture in a ratio of 3: 1 to 1: 3 is used. 11. The method according to claims 1-10, characterized in that pastes added to the feed alcohol. 12. The method according to claims 1-11, characterized in that methanol is added to the starting material. 13. Catalyst, characterized in that it contains the following components: a) 5-80% by weight of zirconium in elemental form and / or in the form of its compounds, b) 5-80% by weight Zn in elemental form and / or in the form of its compounds, c) 1-80 parts by weight of Mn in elemental form and / or in the form of its compounds, d) 0.0001-10 wt .-% of at least one basic and / or convertible into a basic compound compound from the group of alkali and / or alkaline earth metals and / or ammonia and / or the basic and / or convertible into a basic compound Compounds of ammonia. 14. Catalyst according to claim 13, characterized in that it contains the same 20-80Gew .-% Zr. 15. Catalyst according to claims 13 and 14, characterized in that it contains the same 20-80 wt .-% Zn. 16. A catalyst according to claims 13-15, characterized in that it contains the same 10-80Gew .-% Mn. 17. Catalyst according to claims 13-16, characterized in that it contains the same 0.001-5Gew .-% of component d. 18. Catalyst according to claims 13-17, characterized in that the same additional at least one element from groups 1, 2, 3 and 8 subgroup of the periodic table in an amount of 0.001 to 10Gew .-%, preferably from 0 , 01-2Gew .-% in elemental form and / or in the form of its compounds. 19. A catalyst according to claims 13-17, characterized in that it contains in addition 0.001 to 10 wt .-%, preferably 0.01-2Gew .-% palladium in elemental form and / or in the form of its compounds. 20. Catalyst according to claims 13-19, characterized in that it contains the components zirconium, zinc and manganese in the form of oxides.