FR2627484A1 - Prodn. of mixt. of methanol and higher alcohol(s) from synthesis gas - on catalyst with solid support of zinc oxide or zinc aluminate carrying nickel and molybdenum and opt. other metals - Google Patents

Abstract

A mixt. of methanol and higher alcohols is prepd. by contacting synthesis gas with a S-free catalyst prepd. by (A) impregnating a support with a Ni cpd., a Mo cpd., and opt. a cpd. of Li, Na, K, Rb, Cs and/or Be (I), where the metals are introduced together or separately as soln(s)., and the support is a solid Zn cpd., with specific surface at least 10 square m/g comprising ZnO, a stoichiometric Zn aluminate (ZnAl2O4), A Zn aluminate with a stoichiometric excess of Zn (ZnAl2O4.nZnO, where n = 0.01-10), or a mixed Zn aluminate of formula Zn1-xMxAl2O4 or ZnAl2O4.(n-y)ZnO.MOy, (B) drying, and (C) heat-activating. x = 0.01-0.5; y = 0.01-5; M = Mg, Zr, Ca, Sr, Ba, Co or Cu. USE - The alcohols are used in petrochemistry (prodn. of olefins, ethers, aldehydes, acids) or pure chemistry (prodn. of esters), but the main appln. is in fuels, utilising the good octane properties.

Description

 The present invention relates to the production of mixed alcohols from synthesis gas, in the presence of a specific catalyst containing nickel, molybdenum and a zinc-based support. These alcohols have many petrochemical applications (for example production of olefins, ethers, aldehydes, acids) or in fine chemistry (for example production of esters) but their main application is fuel use. -with their excellent octane properties.

 Many methods have been proposed for the production of oxygenates such as alcohols from CO, CO2, H2 synthesis gas. Specifically, the use of nickel-based catalysts for the synthesis of alcohols includes: US-4582858 which discloses catalysts consisting of nickel, copper, an alkali metal or alkaline earth metal and at least one metal M of groups II to VII of the periodic table. M metals whose use is mentioned are magnesium, calcium, zinc, boron, aluminum, lanthanum, silicon, germanium, titanium, tin, zirconium, vanadium, chromium and manganese.

 Another patent US-4673693 more specifically describes catalysts consisting of copper, nickel, zinc and potassium.

Finally, European Patent EP-0216472 discloses attrition-resistant catalysts, consisting of molybdenum sulfides, a metal such as Nb, Ta, Mo, W, Tc, or Re and optionally one or more Fe Ni metals. Co La Ce Sm Th Na K Zn Mg
Ca. Preferred sulfides contain Mo and / or W as well as cobalt and an alkali metal.

 Such catalysts generally have various disadvantages. the thermal stability of those containing appreciable quantities of copper (by appreciable amount means at least 4% copper relative to the total weight of metals) is not always entirely satisfactory; when those containing sulfur in the form of sulphides, the high hydrogen pressures in the synthesis loop generally cause losses of sulfur, by balanced formation of hydrogen sulphide (H2S). This usually requires continuous injection of H2S into the makeup gas makeup flow.

The gaseous purge and the produced alcohols are generally polluted by sulfur (H2S, mercaptans, others).

 The method of the invention, which aims to overcome the above drawbacks, uses as catalyst a solid material, substantially free of sulfur and prepared by - at least one impregnation (step A) of a support by at least one composed of nickel and at least one molybdenum compound with optionally one or more metal compounds (A) of the group lithium, sodium, potassium, rubidium, cesium and beryllium, said compounds being introduced together or separately as a solution in one or more solvents; said support being a solid mineral compound comprising zinc, having a specific surface area of at least 10 m 2 g-1 and selected from the group consisting of zinc oxide ZnO, stoichiometric zinc aluminate ZnA1204, an over-stoichiometric zinc aluminate ZnAl2O4 zinc, nZnO with n = 0.01 to 10, and a mixed zinc aluminate of formula Zn1 ~ xMxAl2O4 or ZnAl2O4, n-yZnO, MOy, with x = 0.01 - 0.5 and y = 0.01 And M being chosen from the group formed by magnesium, zirconium, calcium, strontium, barium, cobalt and copper.

- At least one drying (step B) - at least one thermal activation (step C) of said catalyst.

 Preferably the nickel and molybdenum metals are between them in an atomic ratio of from 0.1: 1 to 1.2: 1, and preferably from 0.25: 1 to 1: 1; this whatever their concentrations in the catalyst.

The preferred M metals are magnesium, zirconium, calcium, strontium and barium. The composition of the abovementioned catalysts, expressed as a mass percentage of metal relative to the total mass of metals, corresponds to the following concentration ranges
2 to 30% nickel
2 to 30% molybdenum
10 to 95% zinc
0 to 60% aluminum
0 to 30% magnesium and / or zirconium
O at 15% calcium, and / or strontium and / or barium
0 to 25% cobalt
0 to 1% copper and 0 to 7% metal A.

In a preferred manner, said catalysts are
3 to 15% nickel,
3 to 15% molybdenum
20 to 95% zinc
0 to 50% aluminum and at least one metal M, said metal then being in the proportions
3 to 20% for magnesium and / or zirconium
3 to 12% for calcium, and / or strontium and / or barium and 0 to 4% of metal A.

 The preferred metals A are potassium, rubidium and cesium. To prepare the catalyst, starting from a carrier as defined above.

When zinc is used in the form of zinc oxide, it is preferred to use commercial oxides or oxycarbonates having a specific surface area of at least 20 and preferably of at least 50 m 2
When the zinc is used in the form of a zinc aluminate, the latter will preferably be prepared by using a suitable coprecipitation method as described, for example, by the Applicant in Studies in Surface Science and Catalysis Vol.31 p.739 1987; so that this support has a specific surface area of at least 10 m2g-1 and preferably at least 40 m2 -1. The active elements nickel, molybdenum and optionally M are added to the support in the form of one or more aqueous solutions or organic salts or compounds of the aforementioned metals.

 Soluble oxides, hydroxides, carbonates, hydroxycarbonates which are soluble in an acidic medium or ammoniacal medium in the form of amine complexes may be used, for example; nitrates, oxalates, tartrates, citrates, acetates, acetylacetonates or anionic combinations; the nitrates are, in an aqueous medium, the soluble salts which are most often used. In organic medium, it is possible to use, for example, acetylacetonates or even naphthenates.

 The support may have previously been shaped (eg beads, extrusions, pellets); the solutions are then added by any impregnation process, as known to those skilled in the art.

 The support may also be used in the form of a powder, with a mean particle size of 0.1 to 1000 m, the solutions, preferably aqueous in the latter case, are added by any wet kneading process known to the man of the invention. Art; the paste obtained being subsequently shaped by any method (atomization, coagulation into drops, extrusion, etc.) or dried and then shaped by any method (pelletizing for example).

The addition of nickel, molybdenum and possibly metals M to the support containing the zinc can be done by a single impregnation (step A). To this end, it will be useful to add compounds known to those skilled in the art allowing solution compatibility of molybdenum, nickel and M metals such as hydrogen peroxide, an alkanolamine or an alcoholic acid; the impregnated support is then dried (step B) and then thermally activated (step
C). When nickel, molybdenum, optional M metals are added separately to the support, it is possible, for example, to first impregnate a nickel salt, for example the nitrate (step A) and then dry (step B); then impregnate a molybdenum salt, for example ammonium ltheptamolybdate (step A) and then dry (step B), possibly reproduce the same sequence (AB) to add at least one metal M, then finally thermally activate (step C). It is also possible, this is not critical, to add a thermal activation step between each impregnation (ABC ABC sequences) As known to those skilled in the art, the impregnations can be adjusted to the pore volume of the support used ( dry impregnation) or be conducted with an excess of solution, which is depleted of metals in contact with the support.

 The order of addition of the nickel, the molybdenum, the possible metals M is indifferent.

The drying is generally carried out between about 50 and about 200 ° C., for a time sufficient for the final water content of the dried product to be less than 10% and preferably 5% by weight; thermal activation is generally between about 300 and about 600 percent for at least one hour; the two steps can be chained. Drying and / or thermal activation modes, whether static or dynamic, are suitable; These two steps are usually conducted under air sweep (VVH 50 to VVH 5000 h1;
FNT).

 The metals A which may optionally be added to the catalyst may be added at any stage of the manufacture of said catalysts. Thus, at least one metal A can be added in the form of soluble molybdate (for example potassium molybdate) and impregnated on the zinc-based support; an aqueous solution of at least one metal compound A (for example carbonate, hydrogencarbonate, hydroxide, nitrate) or organic compound of at least one metal compound A (for example alkoxide, naphthenate, etc.) can also be impregnated onto the dried product (after step B) or thermally activated (after step C).

 The conditions of use of said catalysts for the fabrication of alcohols are usually as follows: the catalyst, charged to the editor, is first reduced by a mixture of inert gas (for example nitrogen) and at least one reductive compound chosen in the group consisting of hydrogen, carbon monoxide, C 1 and C 2 alcohols and aldehydes, the molar ratio of reducing compound / reducing compound + inert gas being from 0.001: 1 to 1: 1.

 The reduction temperature generally varies from 200 to 600 C. but preferably from 300 to 5500 C. The total pressure is usually between 0.1 and 5 MPa and preferably between 0.2 and 2 MPa; the hourly volumetric rate is usually from 0.5 × 10 2 to 1 × 10 4 h -1 and preferably from 1 × 10 2 to 5 × 10 3 hr (N.P.N.).

The actual synthesis reaction of the alcohols is carried out under the following operating conditions
The total pressure is usually between 2 and 25 MPa and preferably between 5 and 15 MPa.

 The partial pressure of (H2 + CO + CO2) will usually be between 2 and 15 MPa and preferably between 5 and 12 MPa.

As will be said hereinafter, the average molar ratio
H2 / CO in the reaction zone, defined as the average of the reactor inlet and outlet ratios, is 0.5: 1. at 4: 1, but preferably from 0.2: 1 to 3.5: 1; the average temperature in the reactor is 250 to 350 ° C and preferably 260 to 320 ° C
The hourly volume velocity (expressed in TPN volume of gaseous mixture per volume of catalyst per hour) is usually between 1000 and 40,000 hi and preferably between 2000 and 20,000 h 1.

 The catalyst can be used in fine-graded powder (10 to 700 micrometers) or in particles of equivalent diameter 2 to 10 mm, in the presence of a gaseous phase, or a liquid phase (under operating conditions) and a gas phase. The liquid phase may consist of one or more hydrocarbons having at least 5 and preferably at least 10 carbon atoms.

 In this embodiment, it is preferable that the superficial velocities of the gas and the liquid, under the temperature and pressure conditions of the process, be at least 1.5 cm / sec.

and preferably at least 3 cm / sec. By superficial velocity is meant the ratio of the volume flow to the section of the reactor considered empty of catalyst.

 Since the synthesis of alcohols is a very strongly exothermic reaction, it may be advantageous to limit the conversion (per pass) of carbon monoxide (CO) to approximately 5-25% and, after condensation of the liquids produced by the reaction, to proceed to least partially to a recycling of the unprocessed gases so as to transform 85% to 95% of the CO contained in the make-up gas.

 In order to limit the quantity of water formed, in parallel with the alcohols produced, it may be advantageous to remove a portion of the CO 2 formed during the reaction (for example by decarbonation with a suitable CO 2 solvent medium) after condensation of the liquids and before proceeding to recycle, at least in part, the aforementioned gas.

 Although the catalysts according to the invention can be used in the presence of synthesis gas (H2 + CO + CO2) containing up to 15% and preferably up to 10% by volume of CO2, it may be advantageous to limit the concentration C02 average at 0-5% and preferably 0.1-3% by volume in the reactor, so as to convert by conversion a maximum of the water formed in parallel with the alcohols and / or hydrocarbons and to simplify the dehydration procedure of said alcohols. The crude alcohols then produced generally contain from 0.1 to 10% by weight of water and more particularly from 0.5 to 5% by weight.

 In order to achieve the same objective, it may also be advantageous to adjust the molar ratio H2 / CO in the reactor between 0.2 and 3.5 and more particularly between 0.5 and 2.8.

 For other details concerning in particular the reduction of the catalyst, the nature of the reactors usable and the nature of the reactions involved, reference may be made to the published European patent application n00238399.

 The following examples describe various aspects of the invention without, however, limiting its scope.

First of all, the preparation of catalysts A to
L whose characteristics are shown in Table I.

CATALYST A
259 of nickel nitrate hexahydrate is dissolved in water. This solution with a volume equal to 2 times the pore volume of the support is used to impregnate 70 g of alumina carrier GFS 400 (Rhone Poulenc) in the form of extrudates 1.2 to 2 mm in diameter. Half of this solution is used to carry out a first dry impregnation (step A) by slow evaporation at 80 ° C. followed by drying at lletuve at 1200 ° C. for 3 hours (step B) and thermal activation for 5 hours at 400 ° C. (Step C), this ABC sequence being renewed with the other half of the solution with a final calcination (step C) for 8 h at 4000C.

CATALYST B
This catalyst is prepared according to the same protocol as the catalyst A (709 GFS 400 support) but replacing the nickel nitrate solution with an aqueous solution containing 126.9 g of ammonium heptamolybdate tetrahydrate and a volume equal to 2 times the pore volume of the support.

CATALYSTS C and D
The extruded GFS 400 alumina support (70 g) is impregnated in 3 times (ABC ABC ABC sequence) with a solution of a volume equal to 3 times the pore volume of the support and containing both the nickel and molybdenum salts as well as monoethanolamine (10 ml) pre-mixed with distilled water.

The impregnating solution is slowly evaporated to dryness at 80 ° C. (stage A) and then the impregnated solid is dried in an oven for 2 hours at 120 ° C. (step B) and calcined for 3 hours at 4000 ° C. (step C), the final calcination being (operated for 8 hours at 400 C. The quantities of salts used are the following
Catalyst C: T7.53 g nickel nitrate hexahydrate
85.05 g of ammonium heptamolybdate tetrahydrate
Catalyst D: 9.51 g of nickel nitrate hexahydrate
73.07 g of ammonium heptamolybdate tetrahydrate
CATALYSTS E, F, H
These catalysts are prepared by separate impregnations of nickel and molybdenum.

 The support is first impregnated in 3 times with a solution of nickel nitrate hexahydrate with a volume equal to 3 times the pore volume of support used (steps ABC ABC ABC) and then 3 times with the aqueous solution of heptamolybdate of ammonium tetrahydrate with a volume equal to 3 times the pore volume (ABC ABC ABC sequence).

 The evaporation is carried out at 80 ° C., the drying (step B) in an oven for 2 hours at 120 ° C. and the calcinations for 3 hours at 400 ° C. except for the final calcination which is carried out for 8 hours at 4000 ° C.

The quantities of products used are as follows
Catalyst E: 80g ZnO specific surface
5 m2 / g (Prolabo)
13.09 nickel nitrate hexahydrate
101.29 of ammonium heptamolybdate tetrahydrates
CATALYST F
809 Lanthanum Oxide (Fluka)
10.7g nickel nitrate hexahydrate
84.2g of ammonium heptamolybdate tetrahydrate
CATALYST H
70g zinc oxide large area
(Old Mountain of France, 70 m2 / g)
14.9g nickel nitrate hexahydrate
9Q, 2g ammonium heptamolybdate tetrahydrate
CATALYST G
This catalyst is prepared according to a protocol identical to that used for the preparation of catalysts C and D with regard to the impregnation of nickel and molybdenum (sequence of steps
ABC ABC ABC), the last calcination (stage C) being carried out for 3 h at 400 C instead of 8 h. The cesium is then incorporated separately by dry impregnation by again following the steps ABC, with a final calcination for 8 h at 400 C.

The amounts of carrier and salts used are as follows
70g alumina GFS 400
10.7g of nickel nitrate hexahydrate
69.79 ammonium heptamolybdate tetrahydrate
0.66g of cesium nitrate
CATALYST I
The protocol followed is strictly identical to that of the catalyst G in which the alumina was replaced by zinc oxide large surface (Old Mountain of France, 70 m2 / g). The amounts of nickel, molybdenum and cesium salts used for 70 g of support are also identical.

The amounts of nickel, molybdenum and cesium salts used for 70 g of support are likewise identical.

CATALYST J
This catalyst has the same formulation as catalyst H, but was prepared from an aqueous solution containing nickel nitrate, ammonium heptamolybdate and monoethanolamine (10 ml) according to the protocol used for the catalysts C and D.

The amounts of salts used for 809 ZnO large surface support (70 m 2 / g) are
17.19 nickel nitrate hexahydrate
103.19 ammonium heptamolybdate tetrahydrate
CATALYST K
The zinc aluminate support, of formula IZnO + ZnA1204, is first prepared by coprecipitation of the corresponding nitrates according to the operating method indicated in "Studies in
Surface Science and Catalysis ", Vol 31, p 739, 1987. This specific surface powder support 105 m 2 / g is then impregnated with an aqueous solution containing the nickel and molybdenum salts according to the protocol used for the catalyst H. quantities of salts used for 70 g of support are as follows
14.9 g of nickel nitrate hexahydrate
90.2 of ammonium heptamolybdate tetrahydrate
CATALYST L
The contents of nickel and molybdenum and the operating method used for the preparation of this catalyst are identical to those of catalyst K. The support is on the other hand of formulation 1.5 ZnO + 0.5CaO + 1ZnA1204 and is previously prepared from the aluminum nitrate, zinc, calcium by coprecipitation according to the operating method stated in "Studies in Surface Science and
Catalysis "Vol 31, p 739, 1987.

Catalyst tests
The catalysts of Examples A to L were tested in a pilot unit operating continuously and operating on 50 ml of catalyst. The unit is fed from a synthetic mixture of gases whose relative proportions of H2-CO-C02 are very close to those measured in industrial unit; it includes partial recycling of the unprocessed gases.

Before testing the catalysts are reduced beforehand under the following conditions
Reduction up to 240 C
- 2% hydrogen in nitrogen
- atmospheric pressure
- hourly volumetric speed: 1500 h-1
- 18h to 1600c steps
18 h to 190 C
5 ha 210 C
2 hours at 240 C
- speed of temperature rise
6 C / h between each ealier
Reduction above 240 C
- 8% hydrogen in nitrogen
- atmospheric pressure
- hourly volumetric speed 3000 h-1
- 1 hour increments at 240 C
1 h to 300 C
1 h to 400 C
1 hour at 500 C
- rate of rise in temperature
12 C / h between each level.

 The catalysts are then tested in the presence of synthesis gas (H2 / CO / CO2) at VVH = 4500 h -1 and P = 5 MPa.

Examples of use Nos. 8 to 12 of catalysts H, I,
J, K, L described in Table III illustrate the performance of the catalysts of the invention.

 Examples of use Nos. 1 to 7 relate to comparison catalysts A, B, C, D, E and F, G.

TABLE 1

<SEP>% <SEP> mass <SEP> of <SEP> metal <SEP> by <SEP> report <SEP> to
<tb> CATALYSTS <SEP> to <SEP> the <SEP> mass <SEP> total <SEP> of <SEP> metals <SEP> Report <SEP> Atomic
<tb> Ni / Mo
<tb> Ni <SEP> Mo <SEP> Zn <SEP> M <SEP> A <SEP> A1 <SEP> The
<tb> A <SEP> Ni / A12O3 <SEP> 12.0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 88 <SEP> 0 <SEP>
B <SEP> Mo / A12 <SEP> O3 <SEP> 0 <SEP> 21.0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 79 <SEP> 0
<tb> C <SEP> NiMo / A12O3 <SEP> 7.5 <SEP> 14.0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 78.5 <SEP> 0 <SEP> 0.88
<tb> D <SEP> NiMo / A12O4.3 <SEP> 12.7 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 83.0 <SEP> 0 <SEP> 0.55
<tb> E <SEP> NiMo / Zn) <SEP> 3.4 <SEP> 10.5 <SEP> 86 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0.55
<tb> F <SEP> NiMo / La2O3 <SEP> 2.8 <SEP> 8.5 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 88.7 <SEP> 0.54
<tb> G <SEP> NiMoCs / A12O3 <SEP> 4.8 <SEP> 2.0 <SEP> 0 <SEP> 0 <SEP> 1.0 <SEP> 82.2 <SEP> 0 <SEP> 0 66
<tb> H <SEP> NiMo / ZnO <SEP> 4.3 <SEP> 10.0 <SEP> 85.7 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0.70
<tb> I <SEP> NiMo / Cs / ZnO <SEP> 4.3 <SEP> 10.0 <SEP> 85.7 <SEP> 0 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 0 66
<tb> J <SEP> NiMo / ZnO <SEP> 4.3 <SEP> 10.0 <SEP> 85.7 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0.70
<tb> K <SEP> NiMo / ZnO, ZnA12O4 <SEP> 4.3 <SEP> 10.0 <SEP> 60.7 <SEP> 0 <SEP> 0 <SEP> 25.0 <SEP> 0 <SEP > 0.70
<tb> L <SEP> NiMo / ZnO, CaO, ZnA12O4 <SEP> 4.3 <SEP> 10.0 <SEP> 59.0 <SEP> 0 <SEP> 19.5 <SEP> 0 <SEP> 0 70
<tb> TABLE 2

Ex. <SEP> Catalyst <SEP> Performance <SEP> CO2 <SEP> H2 / CO <SEP> TC <SEP> r <SEP> SC2 + OH <SEP> SA
<tb> to <SEP> t <SEP> theures <SEP>% <SEP> Vo1
<tb> 1 <SEP> A <SEP> 120 <SEP> 1 <SEP> 1.5 <SEP> 260 <SEP> 0.00 <SEP> 0 <SEP> 0
<tb> 2 <SEP> B <SEP> 120 <SEP> 2 <SEP> 1.5 <SEP> 280 <SEP> 0.02 <SEP> 10.5 <SEP> 12.0
<tb> 3 <SEP> C <SEP> 145 <SEP> 3 <SEP> 1.7 <SEP> 280 <SEP> 0.04 <SEP> 10.5 <SEP> 13.0
<tb> 4 <SEP> D <SEP> 130 <SEP> 2 <SEP> 1.6 <SEP> 280 <SEP> 0.07 <SEP> 20.5 <SEP> 25.5
<tb> 5 <SEP> E <SEP> 120 <SEP> 2 <SEP> 2 <SEP> 260 <SEP> 0.21 <SEP> 22.0 <SEP> 42.0
<tb> 6 <SEP> F <SEP> 130 <SEP> 1 <SEP> 2 <SEP> 280 <SEP> 0.04 <SEP> 12.0 <SEP> 23.0
<tb> 7 <SEP> G <SEP> 145 <SEP> 3 <SEP> 1.7 <SEP> 280 <SEP> 0.23 <SEP> 25.5 <SEP> 58.5
<tb> 8 <SEP> H <SEP> 145 <SEP> 1 <SEP> 2 <SEP> 290 <SEP> 0.56 <SE> 44.5 <SE> 78.5
<tb> 9 <SEP> I <SEP> 145 <SEP> 1 <SEP> 2 <SEP> 280 <SEP> 0.49 <SEP> 49.2 <SEP> 85.5
<tb> 10 <SEP> J <SEP> 120 <SEP> 3 <SEP> 1.7 <SEP> 290 <SEP> 0.48 <SEP> 46.2 <SEP> 70.4
<tb> 11 <SEP> K <SEP> 120 <SEP> 2 <SEP> 1.6 <SEP> 290 <SEP> 0.61 <SEP> 47.3 <SEP> 80.6
<tb> 12 <SEP> L <SEP> 120 <SEP> 2 <SEP> 1.6 <SEP> 290 <SEP> 0.67 <SEP> 42.2 <SE> 83.2
<tb> r = gg-1h-1 SC2 + OH = C2 + OH / (C2 + OH + CH3OH)% by weight
SA see text

Claims (9)

 cobalt and copper.  magnesium, zirconium, calcium, strontium, barium,  0.01-0.5 and y = 0.01-5 and M being selected from the group consisting of  of formula Zn1-xMxA12O4 or ZnA12O4, n-yZnO, MOv, with x =  ZnAl2O4, nZnO with n = 0.01 to 10, and a mixed zinc aluminate  zinc ZnAl2O4, a zinc aluminate surstoechiometric zinc  zinc oxide ZnO, stoichiometric zinc aluminate in  specific of at least 10 m2.g-1 and selected from the group formed  solid mineral compound comprising zinc having a surface  solution in one or more solvents, said support being a  compounds being introduced together or separately in the form of  lithium, sodium, potassium rubidium, cesium and berylium,  optionally one or more metal compounds (A) of the group  nickel compound and at least one molybdenum compound, with  at least one impregnation (step A) of a support by at least one  solid substantially free of sulfur and prepared by  characterized in that a material is used as a catalyst  catalyst, which causes the transformation of said gas into alcohols,  mixture, comprising contacting synthesis gas with a  1. A process for the preparation of methanol and higher alcohols  strontium and barium.  in the group formed by magnesium, zirconium, calcium,  at least one thermal activation (step C) of said catalyst 2. Method according to claim 1, wherein the metal M is chosen  - at least one drying (step B) 3. Method according to claim 1 wherein, expressed in% of  metal relative to the total mass of metals, the catalyst  contains  2 to 30% nickel  2 to 30% molybdenum  10 to 95% zinc  O to 60% aluminum  0 to 30% magnesium and / or zirconium  0 to 15% calcium and / or strontium and / or barium  0 to 25% cobalt  0 to 1% copper  and 0 to 7% of metal A. The method of claim 1 wherein the concentration of  metals is more particularly between  3 and 15% nickel  3 and 15% molybdenum  20 and 95% zinc  O and 50% aluminum  and comprising at least one metal M, said metal being then in the  proportions  3 to 20% magnesium and / or zirconium  and or  3 to 12% calcium and / or strontium and / or barium  and optionally comprising 0 to 4% of metal A. 5. Method according to one of the preceding revendictions, in which  the catalyst before use is reduced by hydrogen or  gaseous mixture containing hydrogen between 200 and 6000C, under  a pressure of 0.1 to 5 MPa and an hourly volumetric velocity of  50 to 10,000 hours 1 (TPN), and  the catalyst, after said reduction, is brought into contact with a  synthesis gas with a molar ratio of hydrogen to carbon monoxide  between 0.5: 1 and 4: 1; at a temperature between 250 and  350 C under a total pressure of between 5 and 15 MPa and one  hourly volumetric speed between 1000 and 40 000 h-1  (TPN); said synthesis gas containing not more than 15% by  volume, carbon dioxide. 6. Method according to one of claims 1 to 5, wherein the  support is shaped before impregnation. 7. Method according to one of claims 1 to 5, wherein the  Catalyst is prepared by at least one impregnation, with mixing  wet, of the support in the form of powder of average grain size  0.1 to 1000 m; the resulting paste being subsequently shaped  by any process. 8. Method according to one of claims 6 or 7 wherein the  Nickel and molybdenum metals are each in an atomic ratio  0.1 / 1 to 1.2 / 1, regardless of their concentrations in the  catalyst. 9. Method according to one of claims 6 or 7 wherein the  Nickel and molybdenum metals are each in an atomic ratio  0.25 / 1 to 1/1, regardless of their concentrations in the  catalyst.