JPH0262535B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a method for producing oxygen-containing organic compounds and paraffinic hydrocarbons from a mixture of carbon monoxide and hydrogen. Oxygen-containing organic compounds such as methanol, ethanol and dimethyl ether are valuable end products and valuable intermediate products for the production of aromatic hydrocarbons and lower olefins, for example. Said oxygen-containing organic compounds can be prepared by catalytic conversion of a mixture of carbon monoxide and hydrogen with a H ₂ /CO molar ratio of at least 0.5. The disadvantage of these reactions is that they are strongly thermodynamically limited so that a significant amount of the H ₂ /CO mixture is not converted. In this method, the higher the space velocity is used, the lower the conversion is obtained. Higher conversions are reached by recycling the unconverted H ₂ /CO mixture, but recycling on an industrial scale is an expensive process that must be avoided if at all possible. That is also true. Furthermore, unconverted
Recirculation of the H ₂ /CO mixture entails other severe disadvantages. The reaction mixture usually contains significant amounts of carbon dioxide in addition to the oxygen-containing organic compounds formed and unreacted carbon monoxide and hydrogen.
This carbon dioxide is produced by a reaction between water and carbon monoxide through a known CO-shift reaction.
The water required for the CO-shift reaction comes from an external source or is generated in the preparation of the oxygen-containing organic compound. Addition of water to the H ₂ /CO mixture to drive the CO-shift reaction is difficult if the available H ₂ /CO mixture is too low.
H ₂ /CO molar ratio. CO−
Due to the shift reaction, the CO content decreases and the H ₂ content increases, resulting in an increase in the H ₂ /CO molar ratio.
The CO-shift reaction can be performed as an external shift (also called pre-shift). The H ₂ /CO mixture to be converted in the external shift is first passed over another CO-shift catalyst with added water before being contacted with a catalyst having the activity of converting the H ₂ /CO mixture into oxygen-containing organic compounds. guided by. In general, the former catalysts generally have CO-shift activity, so in many cases the external shift is omitted and the desired increase in the H ₂ /CO molar ratio of the feedstock is reduced by adding this feedstock to the added water. This can also be easily achieved by introducing the H ₂ /CO mixture onto an active catalyst for the conversion of the H 2 /CO mixture into oxygen-containing organic compounds. If water is produced in the preparation of oxygen-containing organic compounds, the CO− of the latter catalyst
Shift activity is responsible for the production of carbon dioxide.
This is the case if ethers are formed in the preparation of oxygen-containing compounds. To avoid carbon dioxide buildup in the process, carbon dioxide must be removed from the recycle stream. The removal of carbon dioxide from recycle streams on an industrial scale is precisely the recycle itself, which is an expensive process. Applicants have demonstrated high conversion of H ₂ /CO mixtures to valuable compounds by catalytic conversion of H ₂ /CO mixtures without the need for recycling of unconverted H ₂ /CO mixtures and removal of carbon dioxide. We conducted research to find out to what extent it is possible to realize this.
It has been found that this possibility does exist.
For this purpose, the carbon monoxide and hydrogen present in the reaction mixture obtained in the catalytic conversion of the H ₂ /CO mixture to oxygen-containing organic compounds, if desired together with other compounds of this reaction product, are added to the paraffinic It must be contacted with a monofunctional catalyst having catalytic activity for the conversion of the H ₂ /CO mixture to hydrocarbons. The catalyst consists of cobalt supported on a silica support and a metal selected from zirconium, titanium and chromium. _H2 /CO mixtures lower than _1.5 can be used as feedstock for the preparation of paraffinic hydrocarbons
If water has a molar ratio of
It must be added in an amount sufficient to bring the H ₂ /CO molar ratio to a value of at least 1.5 by reaction with CO, and must be added to paraffinic hydrocarbons.
Bifunctional catalyst combinations must be used which, in addition to containing a metal component with catalytic activity for the conversion of H ₂ /CO mixtures, contain one or more metal components with CO-shift activity. No.
If the conversion of H ₂ /CO mixtures is carried out in this method, high space velocities are used to convert H ₂ /CO to oxygen-containing organic compounds and paraffinic hydrocarbons.
Very high conversion rates of the mixture can be reached. The paraffinic hydrocarbons obtained in this process are valuable as final products and as starting materials for carrying out catalytic hydrocarbon conversion processes such as aromatization, isomerization, cracking and hydro-cracking. Therefore, the present invention provides a method for producing an oxygen-containing organic compound and a paraffinic hydrocarbon, including:
In a first step, a mixture of carbon monoxide and hydrogen having a _H2 /CO molar ratio of at least 0.5 is contacted with a catalyst having activity for the conversion of the _H2 /CO mixture into oxygen-containing organic compounds; Moreover, the catalyst comprises zinc oxide and one or more additional components selected from copper, chromium oxide and aluminum oxide, and is present in the reaction product from the first stage in the second stage. 175- with a monofunctional catalyst having activity for the conversion of the H ₂ /CO mixture into paraffinic hydrocarbons, if desired together with other components of the reaction product. A temperature of 275°C and 5-
contact at a pressure of 100 bar, and the catalyst is cobalt supported on a silica support and
consisting of a metal selected from zirconium, titanium and chromium, provided that if the feedstock for the second stage has a H ₂ /CO molar ratio lower than 1.5, H ₂ /CO mol is reduced by reaction with CO. adding to this feed an amount of water sufficient to bring the ratio to a value of at least 1.5, and in addition to the above catalyst having activity for the conversion of the H ₂ /CO mixture to paraffinic hydrocarbons. - a bifunctional catalyst combination which also contains one or more metal components having shift activity is used in the second stage under the abovementioned reaction conditions. The process according to the invention is highly flexible with respect to the ratio of the amount of oxygen-containing organic compound to the paraffinic hydrocarbon that can be prepared. If the intention is to give the highest possible yield of oxygen-containing organic compounds, the conditions under which the first stage of the process is carried out can be chosen such that this desire is met, and the unsubstituted H _{The 2} /CO mixture is converted into paraffinic hydrocarbons in the second stage.
If it is intended to result in high yields of paraffinic hydrocarbons, the conditions under which the first stage of the process is carried out are such that the reaction products of the first stage produce the desired high yields of paraffinic hydrocarbons in the second stage. The amount of unconverted H 2 /CO mixture can be selected to include a sufficient amount of unconverted H ₂ /CO mixture to ensure that. In the process according to the invention, a H ₂ /CO mixture with a H ₂ /CO molar ratio of at least 0.5 is used as feedstock for the first stage. H ₂ /
CO mixtures can be very suitably prepared by steam gastification of carbon-containing materials such as coal. This steam gasification is preferably
It is carried out at a temperature of 900-1500°C and a pressure of 10-100 bar. The preferred _H2 /CO mixture is 0.75-
It has a H ₂ /CO molar ratio of 2.5. If the H ₂ /CO mixture obtained as feedstock for the first stage has a H ₂ /CO molar ratio lower than 0.5, water will be added to the H ₂ /CO mixture by reaction with CO. and _the mixture must be contacted with a catalyst having CO-shift activity. Adding water to the H ₂ /CO mixture and converting the mixture to CO−
Contacting with a catalyst having shift activity is a case in which it is preferred to use H ₂ /CO mixtures with a higher H ₂ /CO molar ratio, and the H ₂ /CO mixture already has a H ₂ /CO molar ratio of at least 0.5. It is also possible if the ratio is The increase in the H ₂ /CO molar ratio can be carried out as a so-called external CO shift.
In this process, the water-containing H ₂ /CO mixture is contacted with another catalyst having CO-shifting activity in a separate step prior to the first step of the process according to the invention. The catalyst used in the first stage of the process according to the invention generally reacts with oxygen-containing organic compounds.
H ₂ /CO when they have CO-shift activity in addition to their activity for the conversion of H ₂ /CO mixtures.
The increase in molar ratio takes place as an internal CO-shift.
In this process the water-containing H ₂ /CO mixture is contacted directly with the catalyst in the first stage of the process according to the invention. If an external CO-shift is used in the process, it is not preferred to perform carbon dioxide removal on the reaction mixture. In the first step of the process according to the invention, the H ₂ /CO mixture, which may contain water and/or carbon dioxide, is contacted with a catalyst having catalytic activity for the conversion of the H ₂ /CO mixture into oxygen-containing organic compounds. In the first stage, H ₂ /
It is preferred to use a catalyst that can substantially convert the CO mixture to methanol or dimethyl ether. Examples of suitable catalysts capable of substantially converting H ₂ /CO mixtures to methanol are (a) zinc oxide and chromium oxide; (b) copper, zinc oxide and chromium oxide; (c) copper, zinc oxide and aluminum oxide. , is a catalyst containing. Examples of suitable catalysts capable of substantially converting H ₂ /CO mixtures to dimethyl ether are methanol synthesis under (a)-(c), such as physical mixtures of gamma alumina and copper, zinc oxide and chromium oxide. one with an acid function and another with an acid function. The first step of the process according to the invention preferably comprises a temperature of 175-350°C and
Pressure of 30-300bar, particularly preferably 225-325℃
and a pressure of 50-150 bar. In the process according to the invention, the carbon monoxide and hydrogen present in the reaction product from the first stage, if desired together with other components of this reaction product, are used as feedstock for the second stage.
If necessary, the entire reaction product of the first stage can be used as feedstock for the second stage. In the second stage according to the invention, as much as possible of the CO present in the feedstock for the second stage is converted to paraffin over a monofunctional catalyst having catalytic activity for the conversion of the H ₂ /CO mixture into paraffinic hydrocarbons. Converted to hydrocarbons. The catalyst consists of cobalt supported on a silica support and a metal selected from zirconium, titanium and chromium. For this,
The _H2 /CO molar ratio in the feed for the second stage should be at least 1.5, preferably 1.75-2.25. High as feedstock for the first stage
If a H ₂ /CO mixture with a H ₂ /CO molar ratio is used, the first step of the process according to the invention is
At least an H ₂ /CO mixture is present and suitable for the conversion over said catalyst in the second stage.
A reaction mixture with a H ₂ /CO molar ratio of 1.5 can be obtained. In the process according to the invention, the reaction product from the first stage is at least 1.5 H ₂ /CO
An attractive approach to ensuring the molar ratio is to add water to the feedstock for the first stage. Thanks to the CO-shift activity of the catalyst in the first stage, this water is removed from the feedstock.
Reacts with CO to form a H ₂ /CO ₂ mixture. 1st
Addition of water to the feedstock for the stage reduces H ₂ /CO from the first stage to less than 1.5 without the addition of water.
If a reaction product with a molar ratio of at least 1.5 is obtained from the first stage even without the addition of water
In both cases where a reaction product having a H ₂ /CO molar ratio is obtained, but it is desired that the feedstock contacted with the catalyst in the second stage has a higher H ₂ /CO molar ratio, The method can be adopted. In the process according to the invention, if a reaction product with a H ₂ /CO molar ratio lower than 1.5 is obtained from the first stage, whether after addition of water to the feedstock for the first stage or not, water must be added to the feedstock for the second stage in an amount sufficient to result in a H ₂ /CO molar ratio at a value of at least 1.5 by reaction with CO, and
In the step, H ₂ / to paraffinic hydrocarbons
Bifunctional catalyst combinations must be used which contain, in addition to a metal component with catalytic activity for the conversion of CO mixtures, one or more metal components with CO-shift activity. The bifunctional catalyst combination which can be used in the second stage of the process according to the invention is preferably composed of two separate catalysts, conveniently designated catalyst A and catalyst B. Catalyst A contains a metal component with catalytic activity for the conversion of H ₂ /CO mixtures to paraffinic hydrocarbons, the metal component being cobalt. Catalyst B contains a metal component having CO-shift activity. Whether a bifunctional catalyst combination or a monofunctional catalyst is used in the second stage according to the invention, it is preferred to use as catalyst A a cobalt catalyst, such as a cobalt catalyst prepared by impregnation. . Very suitable for this purpose is 10−40 pbw per 100 pbw silica.
cobalt and 0.25−5pbw zirconium,
containing titanium or chromium, a silica support is impregnated with an aqueous solution of one or more salts of cobalt and zirconium, titanium or chromium, the composition is subsequently dried and calcined at 350-700°C, and It is a catalyst prepared by reduction at 200-350°C. Appropriate B-
The catalyst is a conventional CO-shift catalyst. Catalysts A and B can be present as a physical mixture in the bifunctional catalyst combination. If the second stage of the process is carried out using a fixed catalyst bed, this bed is continuously made up of alternating 2 catalyst A and catalyst B particles.
made of one or more layers. Along with the use of a bifunctional catalyst conjugate in the second stage, the addition of water to the feedstock for the second stage is recommended if the reaction product of the first stage has a H ₂ /CO molar ratio lower than 1.5 and Both when the reaction product of the first stage already has a H ₂ /CO molar ratio of at least 1.5, but when the feedstock that contacts catalyst A in the second stage has a higher H ₂ /CO molar ratio. It can be used in the method of this invention if that is desired. The second step of the method according to the invention is
It is carried out at a temperature of 175-275°C and a pressure of 5-100 bar. The oxygen-containing organic compounds produced in the two-stage process can very suitably be used as starting materials for the catalytic conversion to lower olefins and/or aromatic hydrocarbons. This conversion preferably converts the oxygen-containing organic compound at a temperature of 300-600°C, a pressure of 1-50 bar and 0.2-15 Kg·Kg ^-1 ·hr.
It is carried out by contacting a crystalline metal silicate as a catalyst at a space velocity of ^-1 . Preferably, a pressure of 1-10 bar is used in this conversion. Very suitable catalysts for the conversion of oxygen-containing organic compounds are those which, after calcination for one hour in air at 500°C, have the following properties: (a) thermally stable up to a temperature of at least 600°C; (b) X-ray powder diffraction image showing the four lines given in Table A as the strongest lines, Table A d(kt) specific intensity 11.1±0.2 VS 10.0±0.2 VS 3.84±0.07 S 3.72±0.06 S Table The letters used have the following meanings: VS: very strong; S: strong;
In formulas indicating the presence of one or more oxides of a trivalent metal A selected from the group formed by iron, gallium, rhodium, chromium and scandium, the SiO ₂ /A ₂ O ₃ molar ratio ( (hereinafter referred to as m in this patent application)
is greater than 10. These crystalline metal silicates will be referred to hereinafter as "Type 1 silicates" in this patent application. The expression "thermally stable up to a temperature of at least t°C" as used in this patent application means that the X-ray powder diffraction pattern of the silicate does not substantially change when the silicate is heated to a temperature of t°C. means.
"Type 1 silicates" are the following compounds: one or more compounds of alkali metals (M), one or more compounds containing quaternary organic cations (R), one or more silicon It can be prepared starting from an aqueous mixture comprising a compound and one or more compounds in which a trivalent metal A selected from the group formed from aluminium, iron, gallium, rhodium, chromium and scandium is present. The preparation of "type 1 silicates" is carried out by maintaining the mixture at elevated temperature until the silicate is formed, separating it from the mother liquor and calcining it. In the aqueous mixture from which the "type 1 silicate" is prepared, the various compounds are present in the following ratios, expressed in moles of oxide: _M2O : _SiO2 = 0.01-0.35, _R2O : _SiO2 = 0.01-0.4, It must exist with SiO ₂ :A ₂ O ₃ >10 and H ₂ O:SiO ₂ =5−65. Varying the quaternary organic cations that are mixed into the aqueous mixture creates "Type 1 silicates" that differ in important ways with respect to their overall X-ray diffraction patterns. The total X-ray powder diffraction images of both iron-silicate and aluminum silicate prepared using tetrapropylammonium are given in Table B.

[Table] (D) = One half of the pair
Total X of iron and aluminum silicates prepared using tetrabutylammonium compounds or tetrabutylphosphonium compounds
-line powder diffraction images are given in Table C.

[Table] If "silicates of type 1" are used as catalysts for the conversion of oxygen-containing organic compounds, the preferred choice is silicates containing only one of the above-mentioned trivalent metals, in particular aluminum as trivalent metal. , given to silicates containing iron or gallium. Other catalysts which are very suitable for the conversion of oxygen-containing organic compounds are the following crystalline aluminosilicates: faujasite, zeolite Y, zeolite X, mordenite, erionite, offretite, zeolite. ω, ferririte, chabasite and zeolite ZSM-34.
These crystalline aluminosilicates will be referred to hereinafter as "Type 2 silicates" in this patent application. Other catalysts which are very suitable for the conversion of oxygen-containing organic compounds are ``type 1'' or ``type 2 silicates'' on which one or more catalytically active metals have been deposited by impregnation or ion exchange. It is. These crystalline silicates will be referred to hereinafter as "Type 3 silicates" in this patent application. A preferred choice is given to "type 3 silicates" on which magnesium or manganese is precipitated. If it is intended to substantially convert oxygen-containing organic compounds into aromatic hydrocarbons, the conversion is preferably carried out at a temperature of 300-400°C and at a temperature of 0.5-5 Kg.
The preferred catalysts are "type ¹ silicates ^" where m is less than 200. If it is intended to substantially convert the oxygen-containing organic compound into lower olefins, the conversion is preferably carried out at a temperature of 400-600°C and at a temperature of 1-10 Kg.
At a space velocity of ^-1 h ^-1 , m also acts as a catalyst.
using more than 200 "Type 1 silicates" or at a temperature of 300-500°C, a pressure of 1-5 bar,
It is carried out either at a space velocity of 0.2-2 Kg·Kg ⁻¹ ·h ⁻¹ and using “type 2 or type 3 silicates” as catalysts. For the catalytic conversion of oxygen-containing organic compounds to lower olefins and/or aromatic hydrocarbons,
It is preferred to start from a feedstock of dimethyl ether or a mixture of oxygen-containing organic compounds consisting essentially of dimethyl ether. In addition to C ^- ₄ olefins and C ⁺ ₅ hydrocarbons, C ^- ₄ paraffins are produced in the catalytic conversion of oxygen-containing organic compounds. It is desirable to keep the production of C ^- ₄ paraffins as low as possible during the conversion. Research by the applicant has shown that in catalytic conversion of oxygen-containing organic compounds, the selectivity towards C ^- ₄ paraffins is lower if the oxygen-containing organic compounds are not used directly as feedstock but are diluted. Suitable diluents are especially water, carbon monoxide, _carbon dioxide, hydrogen and ^{C -} _4-4 paraffin. The combination of the process for the catalytic conversion of oxygen-containing organic compounds into lower olefins and/or aromatic hydrocarbons with the two-stage process according to the invention provides that the reaction products from the first stage of the process according to the invention are at least It is attractive because it contains some of the above-mentioned diluents, namely unconverted hydrogen and carbon monoxide and also water and/or dioxide and/or C ^- ₄ paraffins. The combination of the two-stage process according to the invention with a process for the catalytic conversion of oxygen-containing organic compounds to lower olefins and/or aromatic hydrocarbons is carried out in three ways. According to the first embodiment, oxygen-containing organic compounds,
The reaction products from the first stage consist of by-products containing hydrogen, carbon monoxide and carbon dioxide and/or water and/or C ^- ₄ paraffins, one of which is all of the oxygen-containing organic compounds and a small amount of the by-products. The two fractions are separated into at least two fractions, one containing 50% volume and the other containing all of the hydrogen and carbon monoxide. The latter fraction may contain the remainder of the by-products. The plants containing the organic compound containing oxygen are in contact with low -grade olifin and / or aromatic hydrocarbons, and the fractions containing hydrogen and carbon monoxide are contacted in the second stage described earlier in this invention. is converted to In this specific example,
The reaction product from the first stage is preferably separated into two fractions, one containing all of the oxygen-containing organic compounds and all of the by-products, and the other containing all of the hydrogen and carbon monoxide. According to a second embodiment, at least all of the hydrogen, carbon monoxide and oxygen-containing organic compounds of the reaction products from the first stage are always used as feedstock for the second stage of the process according to the invention. used. Optionally, the entire reaction product from the first stage is used as feedstock for the second stage.
Consisting essentially of the oxygen-containing organic compounds produced in the first stage and the paraffinic hydrocarbons produced in the second stage, and in addition to this, in particular unconverted hydrogen and carbon monoxide and water and possible dioxide The carbon-containing reaction product of the second stage can be used directly as feedstock for additional process steps in which the catalytic conversion of oxygen-containing organic compounds to lower olefins and/or aromatic hydrocarbons takes place. Because of the undesirable possibility that some of the C ⁺ ₅ paraffinic hydrocarbons produced in the second stage will be converted to aromatic hydrocarbons in the additional process step, this reaction mixture is Preferably, the C ⁺ ₅ hydrocarbons are separated from the second stage reaction product prior to use as feedstock for the reaction. According to a third embodiment, at least all of the hydrogen, carbon monoxide and oxygen-containing organic compounds of the reaction products of the first stage are combined in an additional process step to convert the oxygen-containing organic compounds into lower olefins and/or aromatic compounds. At any time, it is contacted with a catalyst for conversion to group hydrocarbons. Optionally, the entire reaction mixture from the first stage is used as feedstock for additional process steps. hydrogen, carbon monoxide, C ^- ₄ olefin,
Of the reaction products from the additional process steps, including water and possible carbon dioxide originating from the first stage, at least hydrogen and carbon monoxide are used as feedstock for the second stage of the process according to the invention. must be done. If desired, the entire reaction product from the additional process steps can be used as feedstock for the second stage of the process according to the invention. Before using this reaction product as feedstock for the second stage of the process according to the invention, it is preferred to separate the C ^- ₄ olefin from the reaction product of the additional process step. Applicants have found that if in the second stage of the process the aforementioned cobalt-impregnated catalysts promoted by zirconium, titanium or chromium are used, heavy paraffinic hydrocarbons are obtained which can be prepared by hydrocracking in the middle distillate. It is particularly suitable for high-yield conversion to minutes. Hydrocracking operations are characterized by very low gas production and hydrogen consumption. The invention will now be explained with reference to the following examples. EXAMPLES The following catalysts were used in the study. Catalyst 1 Cu/Zn/Cr atomic ratio of 5:3:2
ZnO/ _{Cr2O3 catalyst} . Catalyst 2 γ-Al ₂ O ₃ calcined at 800°C. Catalyst 3 Cu/ZnO/ with Cu/Zn atomic ratio of 0.55
_{Al2O3 catalyst} . Catalyst 4 25 pbw cobalt per 100 pbw silica and
Co/Zr/ _SiO2 catalyst containing 0.9 pbw of zirconium, which impregnated a silica support with an aqueous solution containing cobalt and zirconium salts, subsequently dried the composition and calcined it at 500 °C. , also made by reducing it at 250℃. Catalyst 5 The crystalline aluminum silicate had the following properties after calcination in air at 500°C for 1 hour. (a) thermally stable up to temperatures of at least 800°C; (b) an X-ray powder diffraction pattern substantially as shown in Table B; (c) representing the composition of the silicate, expressed in moles of oxide; In the formula, the SiO ₂ /Al ₂ O ₃ molar ratio is
It was higher than 10. Catalyst Mixture A physical mixture of Catalyst 1 and Catalyst 2 in a 1:1 weight ratio. Catalyst mixture A layer of catalyst 3 and a layer of catalyst 4 in a volume ratio of 1:2 Catalysts 1 and 4 and the catalyst mixture for the preparation of methanol or dimethyl ether in one stage and paraffinic hydrocarbons and methanol or Tested for the preparation of dimethyl ether. The test is 1
or in a 50-ml reactor containing two fixed catalyst beds. Seven experiments were conducted. Experiments 1, 2, and 4 were performed in one stage, and the other experiments were performed in two stages. A pressure of 60 bar was used in the first stage in all of the experiments. In all of the experiments conducted in two stages, the entire reaction product of the first stage was used as feedstock for the second stage. The feed for the first stage of Experiment 7 was 0.5 H ₂ /
Obtained from a H ₂ /CO starting mixture with a CO molar ratio. Since a large amount of water was added to this _H2 /CO mixture, after performing an external CO-shift on catalyst 3,
A H ₂ /CO molar ratio of 1.0 was reached. CO - formed in the shift CO ₂ (based on the gas mixture
14.3% volume) was not separated. 1.0 _H2 /CO
The H ₂ /CO mixture containing CO ₂ with the molar ratio was
was used as feedstock for the first stage. The results of Experiments 1-7 are listed in Table D. In Run 8, a three-step process was used to convert H ₂ / Simulated for conversion of CO mixture. Experiment 8 The product from the first step of experiment 7 was divided into two fractions,
i.e. fraction A consisting of hydrogen and carbon monoxide with a H ₂ /CO molar ratio of 0.88 and 24.1:
dimethyl ether in a volume ratio of 70.5:5.4,
It can be separated into fraction B consisting of carbon dioxide and water. In experiment 8, the two fractions were converted separately. Fraction A is at a temperature of 240°C, a pressure of 36 bar and a space velocity of 1000 Nl·l ^-1 ·h ^-1 .
0.17 water per catalyst per hour was added onto the catalyst mixture. Conversion of the H ₂ /CO mixture was 87% by volume. Considering the conversion of the H ₂ /CO mixture in the first stage of experiment 7, this means a total conversion of 93% volume of the H ₂ /CO mixture. Fraction B was conducted over catalyst 5 at a temperature of 500° C., a pressure of 1 bar and a space velocity of 1 g dimethyl ether/g catalyst/h. Dimethyl ether conversion was 100%. The hydrocarbons formed had the following composition: 30% by weight of the aromatic-rich C ⁺ ₅ fraction, 60% by weight of the C ^- ₄ olefin infraction, 10% by weight of the C ^- ₄ paraffin fraction, as described above. Of Experiments 1-8, only two-stage Experiments 3 and 5-7 and three-stage Experiment 8 are experiments according to the present invention. Single-stage experiments 1, 2, and 4 are outside the scope of this invention. These are included in this patent application for comparison. Regarding the results listed in Table D, the following points are noted.

【table】

TABLE Experiments 1 and 2 demonstrate one-step production of methanol. In experiment 1, a low conversion of the H ₂ /CO mixture is achieved (41% volume). In comparison with Experiment 1, the space velocity in Experiment 2 was reduced by a factor of 4. The results of experiment 2 show that although this causes an increase in the conversion of the H ₂ /CO mixture (from 41 to 56% by volume), the conversion achieved is higher than that without recycling the unconverted H ₂ /CO mixture. It is still too low to use the method on an industrial scale. Experiment 3 demonstrates the production of methanol and paraffinic hydrocarbons using a two-step process according to the invention. By using the same space velocity as in run 2, a conversion of 94% volume of H ₂ /CO mixture (now based on the total catalyst volume in the first and second stages) is now achieved. Experiment 4 shows a one-step preparation of dimethyl ether. In comparison with experiment 2 (one-step production of methanol), the conversion of the H ₂ /CO mixture is now higher (66% volume instead of 56% volume), but the conversion achieved is lower than that of the unconverted H ₂ /CO It is still too low to use the process on an industrial scale without recycling the mixture. Experiments 5-7 demonstrate the production of dimethyl ether and paraffinic hydrocarbons using a two-step process according to the invention. In comparison with Run 4, in Run 5 the conversion of the H ₂ /CO mixture reaches 93% by weight using the same total amount of catalyst. Experiments 5 and 6 demonstrate a two-step process according to the invention starting from H ₂ /CO mixtures with different H ₂ /CO molar ratios. This experiment shows that the product from the first stage of experiment 5 has a low
Water is added to the feed for the second stage, taking into account the H ₂ /CO molar ratio (1.0). Experiment 7 is Experiment 5
H ₂ /CO with a H ₂ /CO molar ratio of 1.0 used as feedstock for the first stage.
The mixture consists of H ₂ /CO with a H ₂ /CO molar ratio of 0.5.
It was obtained by applying an external CO shift to the mixture and did not remove the CO ₂ produced. As in experiment 5, in experiment 7 a low H ₂ /CO molar ratio of the product from the first stage (0.88)
Considering this, water was added to the feedstock for the second stage.

Claims (1)

[Claims] 1. A method for producing an oxygen-containing organic compound and a paraffinic hydrocarbon, in which, in the first step, a mixture of carbon monoxide and hydrogen having a H ₂ /CO molar ratio of at least 0.5 is added to the oxygen-containing organic compound. contact with a catalyst active for the conversion of a H ₂ /CO mixture to and in a second stage, the carbon monoxide and hydrogen present in the reaction product from the first stage, if desired together with other components of this reaction product, are converted into paraffinic hydrocarbons. contact with a monofunctional catalyst having activity for the conversion of _H2 /CO mixtures at a temperature of 175-275<0>C and a pressure of 5-100 bar;
Moreover, the catalyst consists of cobalt supported on a silica support and a metal selected from zirconium, titanium and chromium, provided that the feedstock for the second stage has an H ₂ /CO molar ratio lower than 1.5. If present, add sufficient water to this feedstock to bring the H ₂ /CO molar ratio to a value of at least 1.5 by reaction with CO, and the addition of H ₂ /CO to the paraffinic hydrocarbons
using in the second stage a bifunctional catalyst combination comprising, in addition to the abovementioned catalyst having activity for the conversion of the mixture, also one or more metal components having CO-shift activity, under the abovementioned reaction conditions; The above method is characterized in that: 2. Process according to claim 1, characterized in that in the first stage of the process a catalyst is used which is capable of substantially converting the _H2 /CO mixture into methanol or dimethyl ether. 3. The first step of the method was carried out at a temperature of 225-325°C and 50°C.
3. The method according to claim 1 or 2, carried out at a pressure of -150 bar. 4 The catalyst with activity for the conversion of the _H2 /CO mixture to paraffinic hydrocarbons used in the second stage of the process is 10-
A catalyst containing 40 pbw of cobalt and 0.25-5 pbw of zirconium, titanium or chromium, with a silica support containing cobalt and zirconium,
Impregnated with an aqueous solution of one or more salts of titanium or chromium, the composition is subsequently dried, calcined at 350-700°C and heated to 200°C.
Process according to any one of claims 1 to 3, produced by reduction at -350<0>C. 5 Adding water to the feedstock for the second stage and converting the second stage into a continuous flow of CO-shift catalyst and particles of a catalyst having activity for the conversion of the H ₂ /CO mixture to paraffinic hydrocarbons. 5. A process according to any one of claims 1 to 4, carried out using a fixed catalyst bed made up of two or more alternating layers. 6. Claim 1, wherein the oxygen-containing organic compound produced in the first stage of the process is catalytically converted into lower olefins and/or aromatic hydrocarbons in the presence of a diluent in an additional process step. 5. The method according to any one of items 5 to 5. 7 Additional process steps at temperatures of 300-600°C, 1
7. The process as claimed in claim 6, carried out at a pressure of -50 bar and a space velocity of 0.2-15 Kg.Kg ^{-1.hr -1} and using a crystalline metal silicate as catalyst. 8 Patent for the production of substantially aromatic hydrocarbons from oxygen-containing organic compounds, in which the catalyst in the additional process step is a "type 1 silicate", the silicate having m less than 200 A method according to claim 6 or 7. 9. For the production of substantially lower olefins from oxygen-containing organic compounds, the catalyst in the additional process step is a "type 1 silicate", the m of which silicate is greater than 200, and the additional process steps at temperatures of 400-600℃ and 1
8. The method according to claim 6 or 7, which is carried out at a space velocity of −10 Kg·Kg ⁻¹ ·hr ⁻¹ .