CA1147749A - Process for the manufacture of oxygen-containing carbon compounds and olefins from synthesis gas - Google Patents
Process for the manufacture of oxygen-containing carbon compounds and olefins from synthesis gasInfo
- Publication number
- CA1147749A CA1147749A CA000354509A CA354509A CA1147749A CA 1147749 A CA1147749 A CA 1147749A CA 000354509 A CA000354509 A CA 000354509A CA 354509 A CA354509 A CA 354509A CA 1147749 A CA1147749 A CA 1147749A
- Authority
- CA
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- Prior art keywords
- rhodium
- olefins
- oxygen
- alkali metal
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
- C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/58—Platinum group metals with alkali- or alkaline earth metals or beryllium
Abstract
Abstract Mixtures consisting of acetic acid, acetaldehyde, ethanol and olefins having two to four carbon atoms are produced from carbon monoxide and hydrogen by catalytic reaction in the gas phase at 1-300 bars and 150°C to 350°C. The oxygen-containing compounds and the olefins are formed in a molar ratio of 1:1 to 2.5:1.
The catalysts contain rhodium, alkali metals and, if appropriate, promoters, on supports.
The supports which have been doped with alkali metal and, if appropriate, with promoters are preferably sintered at temperatures between 400°C and 1,200°C before being impregnated with rhodium.
The catalysts contain rhodium, alkali metals and, if appropriate, promoters, on supports.
The supports which have been doped with alkali metal and, if appropriate, with promoters are preferably sintered at temperatures between 400°C and 1,200°C before being impregnated with rhodium.
Description
~ 7 ~4~
The invention relates to a process for the manufacture of mixtures of oxygen-containing C2 compounds and low-molecular olefins. It relates in particular to the manufacture of mixtures of acetie acid, aeetal-dehyde, ethanol, ethylene and propylene by reactingearbon monoxide with hydrogen in the gas phase.
Theré are already numerous processes known in whieh the gas phase reaction of synthesis gas, that is to say of mixtures of earbon monoxide and hydrogen, on eatalysts containing iron or eobalt, to give mixtures of oxygen-eontaining carbon eompounds and saturated or unsaturated hydroearbons is deseribed This reaetion of synthesis gas, generally known as ~he Fiseher-Tropsch proeess, is not very seleetive, however, and leads to mixtures having a broad and not very speeifie distribution of products in whieh the individual components ean eontain up to 20 or more earbon atoms. Although the addition of .-alkali,espeeially potassium earbonate or potassium oxide, produees a redueed formation of m~ane and an increased formation of olefins in the case of these eatalysts, it r~sults, on the other hand, in an increased growth of ehains, that is to say the formation of higher-molecular eompounds is promoted by the addition of alkaii (eompare B~ssemeier ~t al., Hydrocarbon Processing, Nov. 1976, page 161).
It is also known from German Offenlegungssehrift
The invention relates to a process for the manufacture of mixtures of oxygen-containing C2 compounds and low-molecular olefins. It relates in particular to the manufacture of mixtures of acetie acid, aeetal-dehyde, ethanol, ethylene and propylene by reactingearbon monoxide with hydrogen in the gas phase.
Theré are already numerous processes known in whieh the gas phase reaction of synthesis gas, that is to say of mixtures of earbon monoxide and hydrogen, on eatalysts containing iron or eobalt, to give mixtures of oxygen-eontaining carbon eompounds and saturated or unsaturated hydroearbons is deseribed This reaetion of synthesis gas, generally known as ~he Fiseher-Tropsch proeess, is not very seleetive, however, and leads to mixtures having a broad and not very speeifie distribution of products in whieh the individual components ean eontain up to 20 or more earbon atoms. Although the addition of .-alkali,espeeially potassium earbonate or potassium oxide, produees a redueed formation of m~ane and an increased formation of olefins in the case of these eatalysts, it r~sults, on the other hand, in an increased growth of ehains, that is to say the formation of higher-molecular eompounds is promoted by the addition of alkaii (eompare B~ssemeier ~t al., Hydrocarbon Processing, Nov. 1976, page 161).
It is also known from German Offenlegungssehrift
2,507,6~7 that olefins containing two to four earbon atoms in the molecule c~n be formed preferentially, together with oxy~en-containing compovnds, on catalysts containing 7~ 49
3 --mainly mang~n~se . However, in this process a large part of the carbon monoxide is converted into carbon dioxide; in addition the proportion of oxygen-containing compounds in the reaction mixture is very low.
Recently, numerous processes have also been dis-closed which have as their subject the gas phase reaction o~ synthesis gas on catalysts containing rhodium and which lead, in a high degree of selectivity, to oxygen-containing compounds which preferably have two carbon atoms in the molecule. Such processes have been dis-closed, for example, in German Auslegeschrift 2,503,233, German Auslegeschrift 2,503,204, German Offenlegungsschrift 2,628,463 and U.S. Patent Specification 4,096,164 or have been suggested in German Patent Applications P 2,814,3~5,9, P 2,814,427.6, P 2,825,495.7, P 2,825,59~.3, P 2,850,110.2 and P 2,850,201. 4.
Besides oxygen-containing products having pre-ferably two carbon atoms in the molecule, these processes based on rhodium as the catalytically active component also produce in the main carbon dioxide, methane and only small quantities of other saturated or unsaturated hydro-carbons. Thus, for example, according to M.M. Bhasin et al. (J. of Catalysis 54, 120 (1978)), in the reaction of synthesis gas at 300C and 70 bars on a catalyst con-taining 2.5% by weight of rhodium, only 3.4% of the carbonmonoxide converted react to give saturated and unsaturated hydrocarbons having two or more carbon atoms, while 43.1%
of the carbon monoxide react to give o~ygen-containing C2 compounds and 52% react to give methane.
.
~47~49 By usi-ng catalysts which contain, besides rhodium, also promoters, such as magnesium or manganese, it is possible to obtain the oxygen-containing compounds, such as acetic acid, acetaldehyde and ethanol, in an improved degree of selectivity, Even if the most selective production possible of these oxygen-containing compounds is o~ primary importance in many cases, the simultaneous producti.on of low-molecular olefins, which are indus-trially important primary products of the chemical industry, can, however, be important, particularly if an increas~ forrnation of olefins is associated with the reduced conversion into methane as a by-product.
It has now been found that mixtures of oxygen-containing C2 compounds and a hi~h proportion of low-molecular olefins are obtained if catalysts are usedwhich, besides rhodium and optionally promoters, also contain 0.1 to 5.0% by weight of alkali metals in the form of oxides, hydroxides, salts or complex compounds.
It has been found in addition that the addition of the alkali metal compounds increases the activity of the cata-lys~s and reduces the selective forrnation of methane.
The invention relates, therefore, to a process for the manufacture of mixtures of acetic acid, acetalde-hyde, ethanol and olefins ha~ing two to four carbon atoms, in a 1:1 to 2.5:1 molar rat.io of the said oxygen-containing compounds to the olefins, by reacting carbon monoxide ~nd hydrogen in the presence of catalysts containing rhod..um and op-cionally promoters, in the ~as phase at ternperatures between 150 and 350C and pressures between 1 and 300 bars, ~ .
1147, 49 wherein the catalysts contain 0.1 to 5.0% by weight of alkali metal in the form of oxides, hydroxides, salts or complex compounds.
The result found, that alkali metal ions in low concentrations promote the formation of olefins, reduce ~he conversion of the synthesis gas into methane and additionally increase the total activity of the catalysts, was surprising and could not have been foreseen.
In the process according to the invention, the olefins formed are chiefly ethylene and propylene, as well as small quantities of butenes, and the oxygen-containing compounds formed are acetic acid, acetaldehyde and ethanol and also such products as can be for~ed under the reaction conditions in a secondary reaction, for example by esterification or condensation, above all ethyl acetate and the diethylacetal of acetaldehyde.
The overall selectivity for the formation of oxygen-containing products and olefins is generally between 70 and 90%, relative to carbon monoxide converted. The remainder of the carbon monoxide is converted into alkanes, includinO methane,in~ carbon dioxide and, in small quantities, into oxygen-containing compounds having three or more carbon atoms.
The molar ratio of o~ygen-containing C2 compounds to olefins is between 1:1 and 2.5:1, molar ratio being understood to mean the ratio of the molar sum of the oxygen-containing C2 compounds, that is to say acetic acid, acetaldehyde and ethanol, to the molar sum of the olefins ha~ing 2 to 4 C atoms.
'7'7 Catalysts containing rhodium and optionally promoters and also 0.1 to 5.0,h by weight of alkali cn a support are used for the reaction, according to the invention, of the synthesis gas.
The supports used can be commercially available support materials having a varying specific surface area.
However, supports having a specificsurfacearea of50 to 1,000 m2/g are preferred. Suitable examples are silica, natural or synthetic silicates of elements of the second to eighth group of the periodic system (that is to say, for example, the silicates of magnesium, calcium, aluminum, the rare earths, titanium, zirconium or man-ganese), and also aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, zeolites and spinels.
Rhodium can be present on the carrier in the metallic form or in a valency state less than three, that is to say as a co~plex compound of zero-valent rhodium or as a salt or complex compound of monovalent or divalent rhodium. It is possible to use salts or comp]ex com-pounds of rhodium of any desired valency state as the starting material and, if appropriate, subseauently to c~rry out a reduction stage, such as is described later in the text. Examples of suitable compounds of rhodium are the chlorides, bromides, iodides, nitrates or car-boxylates or double salts of rhodium with alkali metalhalides, such as, for example, dipotassium trichloro-rhodate. Complex compounds which, as well as rhodium and halogen, also contain complex-forming ligands, such as trialkylphosphine, triarylphosphine, ethylenediamine, 11~7749 pyridine, carboll mGnoxide, oleflns or water, are also suitable, that is to say, for example, tris-triphenyl-phosphine-rhodium-I chlorid~ bromide or iodide, tris-triphenylphosphine-rhodium-III chloride, dichloro-bis-ethylenediamine-rhodium-I chloride, tris-ethylenediamine-rhodium-III chloride, bis-tri-o-tolyl-phosphine-rhodium-II chloride, carbonyl-bis-triphenyl-phosphine-rhodium-I
bromide or dicesium carbonyl-pentachlororhodate-III.
In addition, compounds of rhodium,in which it is linked ionically or as a complex to a support,are also suitable.
Examples of these are the zeolites and ion exchangers which have been subjected to an exchange reaction with rhodium halides.
The alkali metal compounds used are the oxides, salts or complex compounds of lithium, sodium, potassium, I~bidium or cesium or mixtures thereof, that is to say, for example, the oxides, hydroxides, carbonates, chlorides, bromides, iodides, nitrates, acetates, silicates and/or aluminates of the alkali metals. The sodium compounds ~0 are par~icularly preferred.
Besides rhodium and alkali metal compounds, the catalysts also preferably contain promoters or activators.-The comblnation magnesium/halide ions and also manganese are particularly suitable as promoters or activators.
If appropriate, however, the catalysts can also contain substances which affect the selectivity of formation of the individual oxygen-containing products, such as iron, zirconium, nafnium, lanthanwm, platinum, mercury, molybdenum and tungsten. The said elements, which are effective as ~i4L'~749 promoters or a~fect the selectivity, can be in the form of simple inorganic or organic compounds, such as, for example, chlorides, bromides, nitrates, carbonates, oxides, hydroxides, silicates or acetates. Complex compounds of these elements containing inorganic or organic ligands, such as, for example, potassium magnesium trichloride, trisodium hexacyanomanganate-III or di-potassium hexacyanoferrate-II, and also chloro-complex compounds of -the said elements with rhodium of the general formula Mem[RhC16]n wherein Me represents one of the said metals, for example Mg3[RhC16]2,are also suitable.
The halide ions used in combination with ~agnesium can be the chlorides, bromides or iodides. The halide can be applied in the form of a rhodium, alkali metal or magnesium compound; suitable compounds have already been mentioned.
It is also possible, however, to employ halogen-~ree magnesium compou~ds, for example the acetates or nitrates, and to apply the halide ions to the support by subsequent treatment with hydrogen halide or impregnation with a metal halide. It is also possible to use an organic compound containing halogen (such as, for example, l,l-dichloroethane) from which the halogen can be libera~ed, in order to adjust the halogen content of the catalyst, after the i~pregnation with the magnesium compound, to the figure necessary for the selective conversion of synthesis gas.
Examples of suitable solvents for the active com-ponents are water and anhydrous or aqueous carboxylic acids, in particular ~a-ter and acetic acid.
.. . .
1~7~ 9 _ g _ In order to build up the catalyst, the support is impregnated, simultaneously or in successive stages in `any desired sequence, with the rhodium compound, the alkali metal compound and, if appropriate, the promoters or the addltives which influence the selectivity.
A particularly preferred form of preparing the catalyst consists in impregnating the support with the solution of the alkali metal compound and of the promoter, drying the mixture, then sintering it at temperatures between 400 and 1,200C and thereafter applying the rhodium compound.
The alkali metal and the promoters can, however, also be incorporated in a substance possessing a lattice structure, for example in a carrier substance containing silicate or aluminum oxide, such as silica, alumir.um oxide or aluminum silicate. A further ad~antageous possible means consists in binding the alkali metal or the promoters by means of ion exchange to cation exchangers which are also suitable as carriers for the rhodiurn and are stable under the experimental conditions, for example the natural or synthetic aluminum silicates which are known as molecular sieves.
Before the catalyst is used for the con~ersion of synthesis gas, it must also be reduced, if the reaction is to take place on metallic rhodiu~ or if trivalent rhodium has been used for the preparation of the catalyst.
The reduction can be carried out in the reactor itself or in a separate apparatus. Examples of suitable reducing agents are hydrogen, carbon monoxide, methanol or acetone. ~eduction temperatures above 300, preferably between 35~ and 550C, produce metallic rhodium; reduction temperatures below 300C, preferably between 100 and 275C, produce a lower (non-metallic) valency state of the rhodium.
Frequently it is expedient not to carry out the reduction using the undiluted reducing agent, but to dilute the ]atter ~lith an additional proportion of inert gas, such as, for example, nitrogen or carbon dioxide.
The concentration of rhodiurn, the alkali metals and, if appropriate, the promoters can vary within wide limits. In general, the values, expressed in terrns of the metals, are between 0.1 and 15% by weight for rhodium, between 0.1 and 5.0% by weight for the alkali metals and between 0.1 and 20% by weight ~or the promoters. If the combination magnesiumjhalide ions is employed, 0.1 -10% by weight of magnesium and 0.1 - 10% by weight o~
halide ions are used. The alkali metal conccntration affects the selectivity of forrnation o~ the olefins and, specifically, the selectivity of forrnation of the olefins increases as the concentration increases.
The process according to the invention is carried out by passing gas mixtures which consist entirely or predominantly of carbon monoxide and hydrogen and, in addi-2~ tion,in somecases can alsocontain other cornponents, such asnitrcgen, argon, carbon dioxide or methane, over the cata-lyst. In -this process the molar ratio of carbon mon-oxide to hydro~en can vary wi-thin wide limits. Molar ratios bet~een 5:1 and 1:5, and particularly between ~:1 and 1:3, are preferred. The reaction -temperatures are, in general, bet~leen 175 and 375C, preferably bet~een 200 and 350C, and the reaction pressures are between 1 and 300 bars, preferably between 10 and 200 bars.
It is expedient to adjust the temperature and pressure to one another in such a way that a high degree of selectivity for the formation of the oxygen-containing compounds is ensured and the exothermic formation of methane, ~hich is favored at higher temperatures, remains slight. High pressures,and temperatures as low as possible will therefore be preferred. The con~ersion of carbon monoxide should generally not exceed 50/0 in this process, since higher conversions can readily lead to an increased formation of by-products, it bein~ also possible for higher-molecular, liquid hydrocarbons and oxygen-containing products to be formed in addition to methane and carbon dioxide.
- The conventional fixed bed rcactors can be used for carrying out the process, and it can be advantageous for improved removal of heat to keep the thickness of the layer of catalyst low. Furthermore, reactors with a moving catalyst bed or fluidized bed reactors are also suitable.
A particularly preferred embodiment of the inven-tion &onsists in carrying out the reaction in a circulating gas apparatus in which the unreacted gas mixture is re-cycled into the reactor after removing the condensible reaction products.
This procedure is particularly economical and, by diluting the fresh gas with the residual gas o~ lower '749 hydrogen content ~lich is fed back as recycle gas, makes possible higher reaction temperatures and thus higher space/time yields at unàltered selectivities.
Recycle gas equipment with an internal or external cir-culation of gas is suitable for this procedure.
The essence of the invention will be illus-trated in the examples which follow, these examples being in~ended in no way to be limiting, Experimental Series A
(The use,of commercially availabl'e supports containing a varying amount of sodium, already present).
Portions of 52 g (120 ml) of the silica supports listed in Table 1 are impregnated at room temperature with a solution of 1,08 g of magnesium chloride hexa-,hydrate in 66 g of ~ater and are then dried for 2 hoursat 80C and for 2 hours at 150C. The supports are then sintered for 30 minutes at 800C. The sintered support is then impregnated at room temperature with a solution of 4.0 g of rhodium-III chloride . x H20 (37.4 by weight of Rh) in 66 g of water and dried in a manner simil~r to that described above. The catalysts are then reduced in a glass vessel by passing 30 l(STP)/hour of hydrogen over them for 3 hours at 225-275C under normal pre~ssure. They contain 2.7% by weight of Rh and 0.24% by weight of Mg.
' 100 ml of the catalyst are put into a stainless .steel reaction tube 810 mm long with an internal diameter o~ 16 mm, which is equipped with a coaxia7 thermoMeter shaathwith an external diameter of 6 ~m. The reactor '74 temperature is adjusted by means of a salt bath.
70 l(STP)/hour of a mixture of carbon monoxide and hydrogen in a 1:1 volume ratio is passed over the catalyst at 20 bars and an internal temperature of 275C.
The reaction mixture is cooled and the incondensible components are allowed to expand. The gaseous com-ponents and the condensed reaction products are determined by gas chromatography. The results listed in Table 1 are obtained.
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__ (The use of suppor~s which have been doped with various alkali metal salts).
The quantities of alkali metal salt indicated in Table 2, ~hich correspond in each case to 8.16 mmoles of the anhydrous compound, are each dissolved in 66 g of ater. These solutions are used to impregnate in each case 52 g (120 ml) of the silica support mentioned in Comparison Example 1 of Experimental Series A. After being impregnated, the support is dried for 2 hours at 80C and for 2 hours at 150C and is finally sintered for 30 minutes at 800C. Each of the supports is then impregnated with a solution of 1.08 g of magnesium chloride hexahydrate in 66 g of water and is dried and sintered in the same manner as described above. The supports pre-treated in this way are then additionally impregnated with a solution of 4.0 g of rhodium-III
chloride.x H20 (37.4% by weight of Rh) in 66 g of water and are dried for 2 hours at ~0C and for 2 hours at 150C and are finally reduced in a glass vessel by passing 30 l(STP)/hour of hydrogen over them for 3 hours at 225-275C under normal pressure. The catalysts contain 2,7% by weight of Rh and 0.24% by weight of Mg.
These catalysts are tested in the reactor des-cribed in Experimental Series A under the reaction con-ditions indicated in that seri es . The results are listed in Table 2.
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(Recycle gas apparatus) The apparatus consists of a heatcd reaction tube with a length of 1 m and an internal diameter of 24.4 mm, made of corrosion-resistant steel and having a coaxial thermometer sh~a ~ ~t,h an external diameter of 12 ~m, a condenser placed do~mstream, a receiver for the condensate and a compressor for recycling part of the non-condensed gases to the reactor (recycle gas), In each case 250 ml of the catalysts described below are charged. After flushing the apparatus with nitrogen, a pressure of 100 bars is initially set up by means of-a synthesis gas ccmposed of 49% by volume of C0, 49% by volume of H2, 1%
by volume of C02 and 1% by volume of N2 (and small quantities of other components) and the reactor is heated to 275C, During the heating-up period and in the further course of the experiments, 1,000 l(STP)/hour of synthesis ~as of the above composition are fed via the suction side of the compressor to the recycle gas and, together with ~he latter, are pass~d over the catalyst, The gas circulation rate is about 5,000 l/hour, The gas mixture leaving the reactor is cooled to about +5C in a brine-cooled condenser and the condensed constituents are collected in the receiver, The non-condensed residual ?5 gas is mixed with fresh synthesis gas and recycled to the reactor via the compressor. Part of the residual gas is bled off through a constant-pressure valve in order to maintain the pressure aIld to remove the olefins and by products. Compariscn Example 3 and EY.amples 11-13 , ~ are carri~d cut by this method. The results are listed in Table 3. The catalyst employed for Comparison Examp]e 3 is 250 ml of the catàlyst mentioned in Comparison Example 1. 250 ml of the catalyst mentioned in Example 4 are used for ~xarnple 11 and 250 ml of the catalyst mentioned in Example 5 are used for Example 12. For Example 13, 250 ml of a catalyst prepared as follows are employed:
120 g of the silica support mentioned in Comparison Example ~, containing 0.04% by weight of Na, are impregnated with a solution of 2.49 g of magnesium chloride hexahydrate and 1. 55 g of sodi~m acetate in 152 g O~ ~later and are dried for 2 hours at 80C, 2 hours at 120C and 2 hours at 150C. The support is then impregnated with a solution of 9.24 g of rhodium-III
chloride (37.4% by weight of Rh) in 152 g of water and is again dried in the same manner as described above.
The catalyst is then reduced in a glass vessel by passing 50 l(STP)/hour of hydrogen over it for 3 hours at 225-275C under normal pressure. The finishcd catalyst contains 2.7% by weight of Rh, 0.240/o by weight of Mg, 0.37% by weight of Na and 1.9~ by weight of C1.
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Recently, numerous processes have also been dis-closed which have as their subject the gas phase reaction o~ synthesis gas on catalysts containing rhodium and which lead, in a high degree of selectivity, to oxygen-containing compounds which preferably have two carbon atoms in the molecule. Such processes have been dis-closed, for example, in German Auslegeschrift 2,503,233, German Auslegeschrift 2,503,204, German Offenlegungsschrift 2,628,463 and U.S. Patent Specification 4,096,164 or have been suggested in German Patent Applications P 2,814,3~5,9, P 2,814,427.6, P 2,825,495.7, P 2,825,59~.3, P 2,850,110.2 and P 2,850,201. 4.
Besides oxygen-containing products having pre-ferably two carbon atoms in the molecule, these processes based on rhodium as the catalytically active component also produce in the main carbon dioxide, methane and only small quantities of other saturated or unsaturated hydro-carbons. Thus, for example, according to M.M. Bhasin et al. (J. of Catalysis 54, 120 (1978)), in the reaction of synthesis gas at 300C and 70 bars on a catalyst con-taining 2.5% by weight of rhodium, only 3.4% of the carbonmonoxide converted react to give saturated and unsaturated hydrocarbons having two or more carbon atoms, while 43.1%
of the carbon monoxide react to give o~ygen-containing C2 compounds and 52% react to give methane.
.
~47~49 By usi-ng catalysts which contain, besides rhodium, also promoters, such as magnesium or manganese, it is possible to obtain the oxygen-containing compounds, such as acetic acid, acetaldehyde and ethanol, in an improved degree of selectivity, Even if the most selective production possible of these oxygen-containing compounds is o~ primary importance in many cases, the simultaneous producti.on of low-molecular olefins, which are indus-trially important primary products of the chemical industry, can, however, be important, particularly if an increas~ forrnation of olefins is associated with the reduced conversion into methane as a by-product.
It has now been found that mixtures of oxygen-containing C2 compounds and a hi~h proportion of low-molecular olefins are obtained if catalysts are usedwhich, besides rhodium and optionally promoters, also contain 0.1 to 5.0% by weight of alkali metals in the form of oxides, hydroxides, salts or complex compounds.
It has been found in addition that the addition of the alkali metal compounds increases the activity of the cata-lys~s and reduces the selective forrnation of methane.
The invention relates, therefore, to a process for the manufacture of mixtures of acetic acid, acetalde-hyde, ethanol and olefins ha~ing two to four carbon atoms, in a 1:1 to 2.5:1 molar rat.io of the said oxygen-containing compounds to the olefins, by reacting carbon monoxide ~nd hydrogen in the presence of catalysts containing rhod..um and op-cionally promoters, in the ~as phase at ternperatures between 150 and 350C and pressures between 1 and 300 bars, ~ .
1147, 49 wherein the catalysts contain 0.1 to 5.0% by weight of alkali metal in the form of oxides, hydroxides, salts or complex compounds.
The result found, that alkali metal ions in low concentrations promote the formation of olefins, reduce ~he conversion of the synthesis gas into methane and additionally increase the total activity of the catalysts, was surprising and could not have been foreseen.
In the process according to the invention, the olefins formed are chiefly ethylene and propylene, as well as small quantities of butenes, and the oxygen-containing compounds formed are acetic acid, acetaldehyde and ethanol and also such products as can be for~ed under the reaction conditions in a secondary reaction, for example by esterification or condensation, above all ethyl acetate and the diethylacetal of acetaldehyde.
The overall selectivity for the formation of oxygen-containing products and olefins is generally between 70 and 90%, relative to carbon monoxide converted. The remainder of the carbon monoxide is converted into alkanes, includinO methane,in~ carbon dioxide and, in small quantities, into oxygen-containing compounds having three or more carbon atoms.
The molar ratio of o~ygen-containing C2 compounds to olefins is between 1:1 and 2.5:1, molar ratio being understood to mean the ratio of the molar sum of the oxygen-containing C2 compounds, that is to say acetic acid, acetaldehyde and ethanol, to the molar sum of the olefins ha~ing 2 to 4 C atoms.
'7'7 Catalysts containing rhodium and optionally promoters and also 0.1 to 5.0,h by weight of alkali cn a support are used for the reaction, according to the invention, of the synthesis gas.
The supports used can be commercially available support materials having a varying specific surface area.
However, supports having a specificsurfacearea of50 to 1,000 m2/g are preferred. Suitable examples are silica, natural or synthetic silicates of elements of the second to eighth group of the periodic system (that is to say, for example, the silicates of magnesium, calcium, aluminum, the rare earths, titanium, zirconium or man-ganese), and also aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, zeolites and spinels.
Rhodium can be present on the carrier in the metallic form or in a valency state less than three, that is to say as a co~plex compound of zero-valent rhodium or as a salt or complex compound of monovalent or divalent rhodium. It is possible to use salts or comp]ex com-pounds of rhodium of any desired valency state as the starting material and, if appropriate, subseauently to c~rry out a reduction stage, such as is described later in the text. Examples of suitable compounds of rhodium are the chlorides, bromides, iodides, nitrates or car-boxylates or double salts of rhodium with alkali metalhalides, such as, for example, dipotassium trichloro-rhodate. Complex compounds which, as well as rhodium and halogen, also contain complex-forming ligands, such as trialkylphosphine, triarylphosphine, ethylenediamine, 11~7749 pyridine, carboll mGnoxide, oleflns or water, are also suitable, that is to say, for example, tris-triphenyl-phosphine-rhodium-I chlorid~ bromide or iodide, tris-triphenylphosphine-rhodium-III chloride, dichloro-bis-ethylenediamine-rhodium-I chloride, tris-ethylenediamine-rhodium-III chloride, bis-tri-o-tolyl-phosphine-rhodium-II chloride, carbonyl-bis-triphenyl-phosphine-rhodium-I
bromide or dicesium carbonyl-pentachlororhodate-III.
In addition, compounds of rhodium,in which it is linked ionically or as a complex to a support,are also suitable.
Examples of these are the zeolites and ion exchangers which have been subjected to an exchange reaction with rhodium halides.
The alkali metal compounds used are the oxides, salts or complex compounds of lithium, sodium, potassium, I~bidium or cesium or mixtures thereof, that is to say, for example, the oxides, hydroxides, carbonates, chlorides, bromides, iodides, nitrates, acetates, silicates and/or aluminates of the alkali metals. The sodium compounds ~0 are par~icularly preferred.
Besides rhodium and alkali metal compounds, the catalysts also preferably contain promoters or activators.-The comblnation magnesium/halide ions and also manganese are particularly suitable as promoters or activators.
If appropriate, however, the catalysts can also contain substances which affect the selectivity of formation of the individual oxygen-containing products, such as iron, zirconium, nafnium, lanthanwm, platinum, mercury, molybdenum and tungsten. The said elements, which are effective as ~i4L'~749 promoters or a~fect the selectivity, can be in the form of simple inorganic or organic compounds, such as, for example, chlorides, bromides, nitrates, carbonates, oxides, hydroxides, silicates or acetates. Complex compounds of these elements containing inorganic or organic ligands, such as, for example, potassium magnesium trichloride, trisodium hexacyanomanganate-III or di-potassium hexacyanoferrate-II, and also chloro-complex compounds of -the said elements with rhodium of the general formula Mem[RhC16]n wherein Me represents one of the said metals, for example Mg3[RhC16]2,are also suitable.
The halide ions used in combination with ~agnesium can be the chlorides, bromides or iodides. The halide can be applied in the form of a rhodium, alkali metal or magnesium compound; suitable compounds have already been mentioned.
It is also possible, however, to employ halogen-~ree magnesium compou~ds, for example the acetates or nitrates, and to apply the halide ions to the support by subsequent treatment with hydrogen halide or impregnation with a metal halide. It is also possible to use an organic compound containing halogen (such as, for example, l,l-dichloroethane) from which the halogen can be libera~ed, in order to adjust the halogen content of the catalyst, after the i~pregnation with the magnesium compound, to the figure necessary for the selective conversion of synthesis gas.
Examples of suitable solvents for the active com-ponents are water and anhydrous or aqueous carboxylic acids, in particular ~a-ter and acetic acid.
.. . .
1~7~ 9 _ g _ In order to build up the catalyst, the support is impregnated, simultaneously or in successive stages in `any desired sequence, with the rhodium compound, the alkali metal compound and, if appropriate, the promoters or the addltives which influence the selectivity.
A particularly preferred form of preparing the catalyst consists in impregnating the support with the solution of the alkali metal compound and of the promoter, drying the mixture, then sintering it at temperatures between 400 and 1,200C and thereafter applying the rhodium compound.
The alkali metal and the promoters can, however, also be incorporated in a substance possessing a lattice structure, for example in a carrier substance containing silicate or aluminum oxide, such as silica, alumir.um oxide or aluminum silicate. A further ad~antageous possible means consists in binding the alkali metal or the promoters by means of ion exchange to cation exchangers which are also suitable as carriers for the rhodiurn and are stable under the experimental conditions, for example the natural or synthetic aluminum silicates which are known as molecular sieves.
Before the catalyst is used for the con~ersion of synthesis gas, it must also be reduced, if the reaction is to take place on metallic rhodiu~ or if trivalent rhodium has been used for the preparation of the catalyst.
The reduction can be carried out in the reactor itself or in a separate apparatus. Examples of suitable reducing agents are hydrogen, carbon monoxide, methanol or acetone. ~eduction temperatures above 300, preferably between 35~ and 550C, produce metallic rhodium; reduction temperatures below 300C, preferably between 100 and 275C, produce a lower (non-metallic) valency state of the rhodium.
Frequently it is expedient not to carry out the reduction using the undiluted reducing agent, but to dilute the ]atter ~lith an additional proportion of inert gas, such as, for example, nitrogen or carbon dioxide.
The concentration of rhodiurn, the alkali metals and, if appropriate, the promoters can vary within wide limits. In general, the values, expressed in terrns of the metals, are between 0.1 and 15% by weight for rhodium, between 0.1 and 5.0% by weight for the alkali metals and between 0.1 and 20% by weight ~or the promoters. If the combination magnesiumjhalide ions is employed, 0.1 -10% by weight of magnesium and 0.1 - 10% by weight o~
halide ions are used. The alkali metal conccntration affects the selectivity of forrnation o~ the olefins and, specifically, the selectivity of forrnation of the olefins increases as the concentration increases.
The process according to the invention is carried out by passing gas mixtures which consist entirely or predominantly of carbon monoxide and hydrogen and, in addi-2~ tion,in somecases can alsocontain other cornponents, such asnitrcgen, argon, carbon dioxide or methane, over the cata-lyst. In -this process the molar ratio of carbon mon-oxide to hydro~en can vary wi-thin wide limits. Molar ratios bet~een 5:1 and 1:5, and particularly between ~:1 and 1:3, are preferred. The reaction -temperatures are, in general, bet~leen 175 and 375C, preferably bet~een 200 and 350C, and the reaction pressures are between 1 and 300 bars, preferably between 10 and 200 bars.
It is expedient to adjust the temperature and pressure to one another in such a way that a high degree of selectivity for the formation of the oxygen-containing compounds is ensured and the exothermic formation of methane, ~hich is favored at higher temperatures, remains slight. High pressures,and temperatures as low as possible will therefore be preferred. The con~ersion of carbon monoxide should generally not exceed 50/0 in this process, since higher conversions can readily lead to an increased formation of by-products, it bein~ also possible for higher-molecular, liquid hydrocarbons and oxygen-containing products to be formed in addition to methane and carbon dioxide.
- The conventional fixed bed rcactors can be used for carrying out the process, and it can be advantageous for improved removal of heat to keep the thickness of the layer of catalyst low. Furthermore, reactors with a moving catalyst bed or fluidized bed reactors are also suitable.
A particularly preferred embodiment of the inven-tion &onsists in carrying out the reaction in a circulating gas apparatus in which the unreacted gas mixture is re-cycled into the reactor after removing the condensible reaction products.
This procedure is particularly economical and, by diluting the fresh gas with the residual gas o~ lower '749 hydrogen content ~lich is fed back as recycle gas, makes possible higher reaction temperatures and thus higher space/time yields at unàltered selectivities.
Recycle gas equipment with an internal or external cir-culation of gas is suitable for this procedure.
The essence of the invention will be illus-trated in the examples which follow, these examples being in~ended in no way to be limiting, Experimental Series A
(The use,of commercially availabl'e supports containing a varying amount of sodium, already present).
Portions of 52 g (120 ml) of the silica supports listed in Table 1 are impregnated at room temperature with a solution of 1,08 g of magnesium chloride hexa-,hydrate in 66 g of ~ater and are then dried for 2 hoursat 80C and for 2 hours at 150C. The supports are then sintered for 30 minutes at 800C. The sintered support is then impregnated at room temperature with a solution of 4.0 g of rhodium-III chloride . x H20 (37.4 by weight of Rh) in 66 g of water and dried in a manner simil~r to that described above. The catalysts are then reduced in a glass vessel by passing 30 l(STP)/hour of hydrogen over them for 3 hours at 225-275C under normal pre~ssure. They contain 2.7% by weight of Rh and 0.24% by weight of Mg.
' 100 ml of the catalyst are put into a stainless .steel reaction tube 810 mm long with an internal diameter o~ 16 mm, which is equipped with a coaxia7 thermoMeter shaathwith an external diameter of 6 ~m. The reactor '74 temperature is adjusted by means of a salt bath.
70 l(STP)/hour of a mixture of carbon monoxide and hydrogen in a 1:1 volume ratio is passed over the catalyst at 20 bars and an internal temperature of 275C.
The reaction mixture is cooled and the incondensible components are allowed to expand. The gaseous com-ponents and the condensed reaction products are determined by gas chromatography. The results listed in Table 1 are obtained.
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__ (The use of suppor~s which have been doped with various alkali metal salts).
The quantities of alkali metal salt indicated in Table 2, ~hich correspond in each case to 8.16 mmoles of the anhydrous compound, are each dissolved in 66 g of ater. These solutions are used to impregnate in each case 52 g (120 ml) of the silica support mentioned in Comparison Example 1 of Experimental Series A. After being impregnated, the support is dried for 2 hours at 80C and for 2 hours at 150C and is finally sintered for 30 minutes at 800C. Each of the supports is then impregnated with a solution of 1.08 g of magnesium chloride hexahydrate in 66 g of water and is dried and sintered in the same manner as described above. The supports pre-treated in this way are then additionally impregnated with a solution of 4.0 g of rhodium-III
chloride.x H20 (37.4% by weight of Rh) in 66 g of water and are dried for 2 hours at ~0C and for 2 hours at 150C and are finally reduced in a glass vessel by passing 30 l(STP)/hour of hydrogen over them for 3 hours at 225-275C under normal pressure. The catalysts contain 2,7% by weight of Rh and 0.24% by weight of Mg.
These catalysts are tested in the reactor des-cribed in Experimental Series A under the reaction con-ditions indicated in that seri es . The results are listed in Table 2.
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'74~1 ~eriment;a3 .~erles C
(Recycle gas apparatus) The apparatus consists of a heatcd reaction tube with a length of 1 m and an internal diameter of 24.4 mm, made of corrosion-resistant steel and having a coaxial thermometer sh~a ~ ~t,h an external diameter of 12 ~m, a condenser placed do~mstream, a receiver for the condensate and a compressor for recycling part of the non-condensed gases to the reactor (recycle gas), In each case 250 ml of the catalysts described below are charged. After flushing the apparatus with nitrogen, a pressure of 100 bars is initially set up by means of-a synthesis gas ccmposed of 49% by volume of C0, 49% by volume of H2, 1%
by volume of C02 and 1% by volume of N2 (and small quantities of other components) and the reactor is heated to 275C, During the heating-up period and in the further course of the experiments, 1,000 l(STP)/hour of synthesis ~as of the above composition are fed via the suction side of the compressor to the recycle gas and, together with ~he latter, are pass~d over the catalyst, The gas circulation rate is about 5,000 l/hour, The gas mixture leaving the reactor is cooled to about +5C in a brine-cooled condenser and the condensed constituents are collected in the receiver, The non-condensed residual ?5 gas is mixed with fresh synthesis gas and recycled to the reactor via the compressor. Part of the residual gas is bled off through a constant-pressure valve in order to maintain the pressure aIld to remove the olefins and by products. Compariscn Example 3 and EY.amples 11-13 , ~ are carri~d cut by this method. The results are listed in Table 3. The catalyst employed for Comparison Examp]e 3 is 250 ml of the catàlyst mentioned in Comparison Example 1. 250 ml of the catalyst mentioned in Example 4 are used for ~xarnple 11 and 250 ml of the catalyst mentioned in Example 5 are used for Example 12. For Example 13, 250 ml of a catalyst prepared as follows are employed:
120 g of the silica support mentioned in Comparison Example ~, containing 0.04% by weight of Na, are impregnated with a solution of 2.49 g of magnesium chloride hexahydrate and 1. 55 g of sodi~m acetate in 152 g O~ ~later and are dried for 2 hours at 80C, 2 hours at 120C and 2 hours at 150C. The support is then impregnated with a solution of 9.24 g of rhodium-III
chloride (37.4% by weight of Rh) in 152 g of water and is again dried in the same manner as described above.
The catalyst is then reduced in a glass vessel by passing 50 l(STP)/hour of hydrogen over it for 3 hours at 225-275C under normal pressure. The finishcd catalyst contains 2.7% by weight of Rh, 0.240/o by weight of Mg, 0.37% by weight of Na and 1.9~ by weight of C1.
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~> ~ O ~ Z;~3 ~ 0 X o 0 X ~ J 1 tr: V c~ ~ V P~ ~ r-l r-l ~1 r~ C\l 1
Claims (5)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a mixture of acetic acid, acetaldehyde, ethanol and olefins having two to four carbon atoms in a 1:1 to 2.5:1 molar ratio of the oxygen-containing compounds to the olefins, in which carbon monoxide and hydrogen are reacted in the presence of a catalyst containing rhodium in the gas phase at a temperature between 150 and 350°C and under a pressure between 1 and 300 bars, said catalyst containing 0.1 to 5.0% by weight of at least one alkali metal in the form of oxides, hydroxides, salts or complex compounds.
2. A process as claimed in claim 1 in which the reaction is carried out in the presence of a promoter.
3. A process as claimed in claim 1 in which the alkali metal is sodium.
4. A process as claimed in claim 1, claim 2 or claim 3 in which the catalyst is present on a support which has been doped with the alkali metal compound and sintered at a temperature between 400 and 1,200°C before being impregnated with the catalyst containing rhodium.
5. A process as claimed in claim 2 or claim 3 in which the catalyst is present on a support which has been doped with the alkali metal compound and the promoter and sintered at a temperature between 400 and 1200°C before being impregnated with the catalyst containing rhodium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792924962 DE2924962A1 (en) | 1979-06-21 | 1979-06-21 | METHOD FOR PRODUCING OXYGEN-CARBON COMPOUNDS AND OLEFINS FROM SYNTHESIS GAS |
| DEP2924962.5 | 1979-06-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1147749A true CA1147749A (en) | 1983-06-07 |
Family
ID=6073725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000354509A Expired CA1147749A (en) | 1979-06-21 | 1980-06-20 | Process for the manufacture of oxygen-containing carbon compounds and olefins from synthesis gas |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0021241B1 (en) |
| JP (1) | JPS567727A (en) |
| AU (1) | AU532066B2 (en) |
| CA (1) | CA1147749A (en) |
| DD (1) | DD151621A5 (en) |
| DE (2) | DE2924962A1 (en) |
| PL (1) | PL124585B1 (en) |
| SU (1) | SU1111684A3 (en) |
| ZA (1) | ZA803713B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590217A (en) * | 1982-01-30 | 1986-05-20 | Hoechst Aktiengesellschaft | Process for the manufacture of acetic acid, acetaldehyde and ethanol |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446251A (en) * | 1980-02-15 | 1984-05-01 | Union Carbide Corporation | Process for producing two-carbon atom oxygenated compounds from synthesis gas with minimal production of methane |
| JPS57126433A (en) * | 1981-01-28 | 1982-08-06 | Sumitomo Chem Co Ltd | Preparation of oxygen-containing hydrocarbon from carbon monoxide and hydrogen |
| JPS6039653B2 (en) * | 1983-04-11 | 1985-09-06 | 工業技術院長 | Method for producing oxygen-containing hydrocarbon compound |
| DE3318210A1 (en) * | 1983-05-19 | 1984-11-29 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING MIXTURES FROM ACETIC ACID, PROPIONIC ACID AND BUTTERIC ACID |
| JP5987719B2 (en) | 2013-02-13 | 2016-09-07 | 三菱電機株式会社 | Semiconductor device |
| DE102019213493A1 (en) | 2019-09-05 | 2021-03-11 | Thyssenkrupp Ag | Process for the production of alcohols |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3952039A (en) * | 1974-07-12 | 1976-04-20 | Union Carbide Corporation | Catalytic process for polyhydric alcohols and derivatives |
| NL7610773A (en) * | 1975-09-30 | 1977-04-01 | Union Carbide Corp | PROCESS FOR PREPARING VARIOUS ALCOHOLS. |
| IL50565A (en) * | 1975-09-30 | 1979-09-30 | Union Carbide Corp | Homogeneous liquid phase process for making alkane polyols |
| CA1099296A (en) * | 1977-05-26 | 1981-04-14 | Leonard Kaplan | Enhancing the promoting of a catalytic process for making polyhydric alcohols |
| US4224236A (en) * | 1978-04-04 | 1980-09-23 | Hoechst Aktiengesellschaft | Process for the manufacture of oxygen-containing carbon compounds from synthesis gas |
| DE2960477D1 (en) * | 1978-04-04 | 1981-10-22 | Hoechst Ag | Process for the preparation of oxygenated hydrocarbon compounds starting from a synthesis gas |
| ZA802237B (en) * | 1979-04-24 | 1981-11-25 | British Petroleum Co | Process for the production of c1 to c4 oxygenated hydrocarbons |
-
1979
- 1979-06-21 DE DE19792924962 patent/DE2924962A1/en not_active Withdrawn
-
1980
- 1980-06-11 DE DE8080103236T patent/DE3063870D1/en not_active Expired
- 1980-06-11 EP EP80103236A patent/EP0021241B1/en not_active Expired
- 1980-06-18 DD DD80221940A patent/DD151621A5/en unknown
- 1980-06-20 AU AU59463/80A patent/AU532066B2/en not_active Ceased
- 1980-06-20 ZA ZA00803713A patent/ZA803713B/en unknown
- 1980-06-20 PL PL1980225116A patent/PL124585B1/en unknown
- 1980-06-20 SU SU802937846A patent/SU1111684A3/en active
- 1980-06-20 CA CA000354509A patent/CA1147749A/en not_active Expired
- 1980-06-20 JP JP8301380A patent/JPS567727A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590217A (en) * | 1982-01-30 | 1986-05-20 | Hoechst Aktiengesellschaft | Process for the manufacture of acetic acid, acetaldehyde and ethanol |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0021241B1 (en) | 1983-06-22 |
| SU1111684A3 (en) | 1984-08-30 |
| DD151621A5 (en) | 1981-10-28 |
| AU532066B2 (en) | 1983-09-15 |
| PL225116A1 (en) | 1981-03-27 |
| AU5946380A (en) | 1981-01-08 |
| JPS567727A (en) | 1981-01-27 |
| DE3063870D1 (en) | 1983-07-28 |
| EP0021241A1 (en) | 1981-01-07 |
| ZA803713B (en) | 1981-07-29 |
| DE2924962A1 (en) | 1981-01-29 |
| PL124585B1 (en) | 1983-02-28 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |