NL8006751A - PROCESS FOR PREPARING OXYGEN-BASED ORGANIC COMPOUNDS AND PARAFFINIC HYDROCARBONS. - Google Patents

Description

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PROCESS FOR THE PREPARATION BOX OXYGEN-containing ORGANIC COMPOUNDS AND PARAFFINIC HYDROCARBONS

The invention relates to a process for the preparation of 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 yol as an end product and as an intermediate, for example for the preparation of aromatic hydrocarbons and lower olefins. Said oxygen-containing organic compounds can be prepared by catalytic conversion of mixtures of carbon monoxide and hydrogen with a 1 / CQ mol. ratio of at least 0.5. A drawback of these reactions is that they are highly limited thermodynamically, so that a considerable part of the H 2 / CO mixture is not converted. As higher spatial throughput rates are used in the processes, lower conversions are obtained.

Although a higher conversion can be achieved by recirculating the unconverted H 2 / CC mixture, the use of recirculation on a technical scale is a costly operation which, if at all possible, should be avoided. In addition, recirculation of the unreacted F 2 / CG mixture presents another serious drawback. As a rule, the reaction product contains, besides formed 8 0 0 8 75 1 λ * -2- oxygen-containing organic compounds and unreacted hydrogen and carbon monoxide, a considerable amount of cage dioxide. This carbon dioxide is created by the reaction of water with carbon monoxide according to the known CO-shift reaction.

5 The water required for the CO-shift reaction may originate. from an external source or may have been formed in the preparation of the oxygen-containing organic compounds. The addition of water to the H 2 / CO mixture for the purpose of effecting the CO shift reaction is used if the available H 2 / CC mixture is too low H 2 / CO mole. relationship. According to the CO-shift reaction, the CO content decreases and the H2 content increases, resulting in an increase in the H 2 / CO mole. ratio. The CO-shift reaction can be carried out as an external shift (also referred to as pre-shift), whereby the H? / C0 mixture to be converted together with added water is first passed over a separate CO-shift catalyst. prior to being contacted with the catalyst having activity for the conversion of an E 2 / CO mixture to oxygenated organic compounds. Since the latter catalysts generally also have CO-shift activity, an external shift can be omitted in a number of cases and the desired increase in the E / CO mole can be achieved. ratio of the feed is easily achieved by passing it along with added water over the catalyst which has activity for the conversion of a /ρ / 00 mixture into oxygen-containing organic compounds.

It is also the CO shift activity of the latter catalyst which is responsible for the formation of carbon dioxide if water is formed in the preparation of the oxygen-containing organic compounds. This situation arises if ether formation occurs in the preparation of oxygen-containing organic compounds. To avoid carbon dioxide build-up in the process, the carbon dioxide should be removed from the recirculation stream • 8 0 0 6 7 5 1 Α Λ -3-. The removal of cage dioxide from recirculation flows on a technical scale is, like the recirculation itself, an expensive operation.

5 An investigation was carried out by the Applicant in order to

to examine to what extent it is possible in the preparation of oxygen-containing organic compounds to realize a high conversion of the Hg / CO mixture into valuable organic compounds by catalytic conversion of an H9 / C0 mixture, without recirculation of the unreacted Hg / CQ mixture and removal of carbon dioxide need to be used. It has been found that this possibility does indeed exist. To this end, carbon monoxide and hydrogen present in the reaction product obtained from the catalytic conversion of the Hg / CQ mixture into oxygen-containing organic compounds, optionally together with other components of this reaction product, must be contacted with a monofunctional catalyst containing one or more metal components with 20 catalytic activity for conversion of a Hg / CO

mixture to paraffinic hydrocarbons, which metal components are selected from the group consisting of cobalt, nickel and ruthenium. If the Hg / CO mixture available as feed for the preparation of the paraffinic hydrocarbons has a Hg / 00 mol. ratio of less than 1.5 should be added to this feed more freely in an amount sufficient to react the Hg / CO mol by reaction with CO. ratio to a value of at least 1.5 and a bifunctional catalyst-30 combination must be used which, in addition to the metal components with catalytic activity for the conversion of a Hg / CO2 mixture to paraffinic hydrocarbons, additionally one or more metal components contains with CO-shift activity. By carrying out the conversion of the Hg / co mixture in this way, using a high spatial transfer rate, a very high conversion of the Eij / CO mixture to oxygen-containing organic products can be carried out. compounds and paraffinic hydrocarbons are achieved.

The paraffinic hydrocarbons obtained in the process are valuable as a final product and as a starting material for carrying out catalytic hydrocarbon conversion processes such as aromatization, isomerization, cracking and hydrogenic cracking.

The present patent application therefore relates to a process for the preparation of oxygen-containing organic compounds and paraffinic hydrocarbons, wherein a mixture of carbon monoxide and hydrogen with an H 2 / CO mole. ratio of at least 0.5 is contacted in a first step with a catalyst containing one or more metal components with catalytic activity for the conversion of a 1 / CO mixture to oxygen-containing organic compounds and wherein carbon monoxide and hydrogen are present in the reaction product from the first step, optionally together with other components from this reaction product, are contacted in a second step with a monofunctional catalyst as defined above, it being understood that if the feed for the second step is a mol. ratio of less than 1.5, water is added to this feed in an amount sufficient to react the Hp / CO mol by reaction with CO. ratio to a value of at least 1.5 and that a bifunctional catalyst combination as defined above is used in the second step.

The process of the invention is highly flexible in terms of the ratio of the amounts of oxygenated organic compounds to paraffinic hydrocarbons that can be prepared. If it is the intention to realize the highest possible yield of oxygen-containing organic compounds 55, the conditions under which the first 8 00 6 75 1 * fr -δε tap of the process is carried out can be chosen such that this wish is met and converting the converted H2 / CO2 mixture into paraffinic hydrocarbons in the second step. If the intention is to realize a high yield of paraffinic hydrocarbons, the conditions under which the first step of the process is carried out can be chosen such that the reaction product of the first step contains sufficient unconverted H 2 / C0 mixture to in the second step, to ensure the desired high yield of paraffinic hydrocarbons.

The process according to the invention uses an Hg / CO mixture with an H 2 / CO mole. ratio of at least 0.5 as feed for the first step. Such H 2 / CO mixtures can very suitably be prepared by steam gasification of a carbonaceous material such as coal. The steam gasification is preferably carried out at a temperature of 900-1500 ° C and a pressure of 10-100 bar.

Preferably H 2 / CO mixtures are used with a H 2 / CO mole. ratio of 0.75-2.5 · If the H 2 / CO mixture which is available as feed for the first step, a H 2 / CO mole. ratio less than 0.5, water should be added to the H 2 / CO mixture in an amount sufficient to react the H 2 / CO mole by reaction with CO. ratio to a value of at least 0.5 and should.

The mixture is to be contacted with a catalyze. satator possessing C0 shift activity. The addition of water to the H 2 / C0 mixture and contacting the mixture with a catalyst having C0-shift activity can also be used in cases where the H 2 / CO mixture already has an H 2 / CO mole. . ratio of at least 0.5, but it is desirable to use an H 2 / CO mixture with a higher Hg / CO mole. apply ratio. The increase in the H2 / C0 mole. ratio can be performed as a so-called external C0 shift where the aqueous H 2 / C0 mixture is contacted in a separate 8 0 0 6 / wi -6 step prior to the first step of the process according to the invention Just like a separate catalyst with CO-shift activity. Since the catalysts used in the first step of the process of the invention, as a rule, in addition to their activity for the conversion of an H2 / CQ mixture to oxygenated organic compounds, Having CO-shift activity, the increase of the H 2 / CO mole ratio can also be performed as an internal CO-shift whereby the aqueous H 2 / CO mixture is directly contacted with the catalyst in the first step of the process According to the invention If the process uses an external CO shift, preferably no carbon dioxide removal is applied to the reaction product.

In the first step of the process of the invention, an H2 / CO mixture which may contain water and / or carbon dioxide is contacted with a catalyst containing one or more metal components with catalytic activity for the conversion of an H2 / CO mixture to oxygenated organic compounds. Preferably, in the first step a catalyst is used which is capable of converting an H 2 / CO mixture into mainly methanol or dimethyl ether. Examples of suitable catalysts which have the ability to convert an H 2 / C0 mixture to mainly methanol are catalysts containing: a) zinc oxide and chromium oxide, b) copper, zinc oxide and ohromoxide, c) copper, zinc oxide and aluminum oxide, and d ) copper, zinc oxide and rare earth oxides. Examples of suitable catalysts which have the ability to convert an H 2 / CO mixture to mainly dimethyl ether are catalysts containing one of the methanol synthesis functions mentioned under a) -d) and in addition an acidic function such as a physical mixture of 7-alumina and a composition containing copper, zinc oxide and chromic oxide. The first step of the method according to the invention is preferably carried out at a temperature of 175-350 ° C and a pressure of 30-300 bar and in particular at a temperature of 225-325 ° C and a pressure of 50- 150 bar.

In the process of the invention, carbon monoxide and hydrogen present in the reaction product from the first step, if desired together with other components of this reaction product, are used as feed for the second step. Optionally, the entire reaction product from the first step can be used as feed for the second step. In the second step of the process according to the invention it is the intention that as much of the CO present in the feed for the second step is to be converted into paraffinic hydrocarbons ever a monofunctional catalyst containing one or more metal components with catalytic activity for the conversion of a H ^ / CO

mixture to paraffinic hydrocarbons, which metal components are selected from the group consisting of cobalt, nickel and ruthenium. The Hp / CQ mol serves this purpose. ratio in the feed for the second step to be at least 1.5 and preferably 1.75-2.25. 3 using a Hp / C0 mixture with a high Hp / C0 mol. ratio as feed for the first step, in the process according to the invention a reaction product from the first step can be obtained in which an H 2 / CO mixture prevents a 30 Ά / CO mole. has a ratio of at least 1.5 and is readily eligible to be converted in the second step over said catalyst. An attractive way to ensure in the process according to the invention that the reaction product from the first step is a H 2 / CO mole. ratio of at least 1.5 is adding water to the feed for the first step. Thanks to the CO-shift activity of the catalyst in the first step, this water reacts with CO 5 from the feed to form a Si / CQ mixture. The addition of water to the feed for the first step can be used in the process according to the invention both in cases where, without addition of water, a reaction product from the first step would have been obtained with a 10 H 2 / CO mol. ratio of less than 1.5, as in cases where a reaction product from the first step with an H 2 / CO mole would have been obtained even without adding water. ratio of at least 1.5, but it is desired that the feed contacted with the catalyst in the second step has a higher H 2 / CO mole. relationship.

In the process according to the invention, if or not after adding water to the feed for the first step, a reaction product from the first step is obtained with an H2 / CO mol. ratio of less than 1.5, water should be added to the feed for the second step in an amount sufficient to react the H2 / CO mol by reaction with CO. ratio to a value of at least 1.5 and in the second step a bifunctional catalyst combination must be used which, in addition to the metal components with catalytic activity for the conversion of a Hg / CO mixture to paraffinic hydrocarbons, additionally one or contains more metal components with CO-shift activity. The bifunctional catalyst combinations which can be used in the second step of the process according to the invention are preferably composed of two separate catalysts, which will be referred to as catalysts A and B for convenience. Catalyst A is the catalyst 8 00 3 75 1 -9- which contains the metal components · with catalytic activity for the conversion of a Hg / CO mixture to paraffinic hydrocarbons and which metal components are selected from the group consisting of cobalt, nickel and 5 ruthenium. Catalyst 3 is the catalyst containing the metal components with CO shift activity. Both when using a monofunctional catalyst and when using an unfunctional catalyst combination in the second step of the process according to the invention, preference is given to a cobalt catalyst such as a cobalt catalyst prepared by impregnation, as catalyst A. Very suitable for the present object are catalysts containing 10-40 wt. parts of cobalt and 0.25-5 wt. parts of zircon, titanium or chromium per 100 wt. parts of silica contain 15 which have been prepared by impregnating a silica support with one or more aqueous solutions of salts of cobalt and zirconium, titanium or chromium followed by drying the composition, calcining at 350-700 ° C and reducing at 200 ° C 350 ° C. The usual CO-shift catalysts can be used as catalysts 3. In the bifunctional catalyst combinations, catalysts A and 3 can be present as a physical mixture. When performing the second step of the process using a fixed catalyst bed, this bed is preferably composed of two or more alternating layers of successively particles of catalyst B and catalyst A. Adding water to the feed for the second step the use of a bifunctional catalyst combination in the second step can be used in the process of the invention both in cases where the reaction product from the first step is an H 2 / CO mole. has a ratio of less than 1.5, as in cases where the reaction product from the first step already has an I / CO mole. ratio of at least 1.5, but wherein 3005751-10- it is desired that the feed contacted with catalyst A in the second step has a higher H 2 / CO mole. relationship. The second step of the method according to the invention is preferably carried out at a temperature of 125-300 ° C and a pressure of 1-150 bar and in particular at a temperature of 175-275 ° C and a pressure of 5-100 bar.

The oxygen-containing organic compounds which are prepared in the two-step process can very suitably serve as a starting material for the catalytic conversion to lower olefins and / or aromatic hydrocarbons. This conversion is preferably carried out by the oxygen-containing organic compounds at a temperature of 300-600 ° C, a pressure of 1-50 bar and a -1 -1 15 spatial throughput of 0.2-15 kg.kg.hour in contact with a crystalline metal silicate as catalyst. Preferably pressures of 1-10 bar are used in this conversion.

Very suitable catalysts for the conversion of the oxygen-containing organic compounds are crystalline metal silicates which are characterized in that after one hour of calcination in air at 500 ° C they have the following properties: a) thermally stable to a temperature of at least 600 ° C , b) an X-ray powder diffraction pattern containing the strongest lines of the four lines listed in Table A.

Table A

d (§) Relative intensity 11.1 + 0.2 Z3

10.0 + 0.2 ZS

3.84 + 0.07 S

3.72 + 0.06 S

8 0 0 6 7 5 1 -11- in which the letters used have the following meanings; Z3 = very strong; 3 = strong, and c) in the formula representing the composition of the silicate, expressed in moles of the oxides, and in which, in addition to oxides of hydrogen, alkali metal and silicon, one or more oxides of a trivalent metal A selected from the group formed by aluminum, iron, gallium, rhodium, chromium and scandium, the SiC ^ A ^ O ^ mole is. ratio (referred to as m further in this patent-10 application), greater than 10.

These crystalline metal silicates will be referred to hereinafter as "type 1 silicates" further in this patent application. The term "thermally stable to a temperature of at least t ° C," as used in this patent application 15, means that upon heating the silicate to a temperature of t ° C, the X-ray powder diffraction pattern of the silicate does not substantially change. of type 1 can be prepared from an aqueous mixture containing the following compounds; one or more compounds of an alkali metal (M), one or more compounds containing a quaternary organic cation (R), one or more silicon compounds and one or more compounds in which a trivalent metal A selected from the group consisting of aluminum, iron, gallium, rhodium, chromium and scandium occurs The preparation of the type 1 silicates takes place by keeping 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 silicates are prepared. e present various compounds in the following proportions expressed in moles of the oxides; 8 0 0 6 75 1 -12- M 2 O: SiO 2 = 0.01-0.35, R 20: SiO 2 = 0.01-0.4,

SiO 2: AO,> 10, and 2 2 p H 2 O: SiO 2 = 5-65 5 By varying the quaternary organic cation which is included in the aqueous mixture, type 1 silicates can be obtained which in terms of their full X-ray powder diffraction pattern significant points differ.

The complete X-ray powder diffraction pattern of an iron silicate and of an aluminum silicate, both of which were prepared using a tetrapropylaamonium compound, is shown in Table 3.

Table 3 d (g) Rel, int. d (£) Rel, int.

11.1 100 3.34 (D) 57 10.0 (D) 70 3.70 (D) 31 3.93 1 3.63 16 7.99 1 3.4? <1 7.42 2 3, 43 5 6.68 7 3.34 '2 6.35 11 3.30 5 5.97 17 3.25 1 5.70 7 3.05 8 5.56 10 2.98 11 5.35 2 2.96 3 4.98 (D). 6 2.36 2 4.60 4 2.73 2 4.35 5 2.60 2 4.25 7 2.48 3 4.07 2 2.40 2 4.00 4 (D) = doublet 8003751 -13-

The complete X-ray powder diffraction pattern of an iron silicate and of an aluminum silicate prepared using a tetrabutyl ammonium compound or a tetrabutylphosphonium compound is shown in Table C.

Table G

d (S) Rel, int. d (S) Rel, int.

11.1 100 3.34 65 10.0 70 3.70 20 7.42 2 3.63 <2 6.68 5 3.47 2 6.35 2 3.34 1 5.97 16 3.30 4 5.70 4.1 3 .05 5 5.56 8 2.98 9 4.98 6 2, S6 1 4.60 3 2.60 2 4.35 5 2.48 3 4.25 <1 2.40 2 4.00 <1

When using type 1 silicates as catalysts for the conversion of the oxygen-containing organic compounds, preference is given to silicates 10 which contain only one of the above-mentioned trivalent metals and in particular to silicates which, as trivalent metal, comprise aluminum, iron or gallium contain.

Also very suitable as catalysts for the conversion of the oxygen-containing organic compounds are the following crystalline aluminosilicates: faujasite, zeolite Y, zeolite X, mordenite, erionite, offretite, zeolite fer, ferrierite, chabasite and zeolite ZSM-34. These crystalline aluminosilicates will be further referred to in this patent 3006751-14 as "type 2 silicates".

Also very suitable as catalysts for the conversion of the oxygen-containing organic compounds are silicates of the type 1 or 2 on which one or more catalytically active metals have been applied by impregnation or ion exchange. These crystalline silicates will hereinafter be referred to as "type 3 silicates" in this patent application. Preference is given to type 3 silicates to which magnesium or manganese has been applied.

If it is the intention to convert the oxygen-containing organic compounds to mainly aromatic hydrocarbons, the conversion is preferably carried out at a temperature of 3 CO-400 ° C and a spatial throughput of 0.5-5 kg. kg ".hr." 15 and a catalyst preferably used is a type 1 silicate, m of which is less than 200.

i

If the intention is to convert the oxygen-containing organic compounds to substantially lower olefins, the conversion is preferably carried out, either at a temperature of 400-60 ° C, a spatial throughput of 1-10 kg .kg-1hr "1 and using a type 1 silicate of which m is greater than 200, as a catalyst, or at a temperature of 300-500 ° C, a pressure of 1-5 bar, a room temperature of 25% throughput rate of 0.2-2 kg.kg ".hr" and using a type 2 or 3 silicate as a catalyst.

For the catalytic conversion of oxygen-containing organic compounds to lower olefins and / or aromatic hydrocarbons, the feed is preferably based on dimethyl ether or a mixture of oxygen-containing organic compounds consisting essentially of dimethyl ether. In the catalytic conversion of oxygen-containing organic compounds, in addition to olefins and 35 C * hydrocarbons, C 8 / paraffins are formed. It is desirable in the conversion to suppress paraffin formation as much as possible. An investigation by the Applicant has shown that the selectivity to paraffins in the catalytic conversion of the oxygen-containing organic compounds is lower if the oxygen-containing organic compounds are used as feed, not diluted as such. Examples of diluents are water, carbon monoxide, carbon dioxide, hydrogen and paraffins.

The combination of the two-step process according to the invention with a process for the catalytic conversion of oxygenated organic compounds to lower olefins and / or aromatic hydrocarbons is particularly attractive because the reaction product from the first step of the process according to the invention has at least some of the aforementioned diluents, namely, unreacted hydrogen and carbon monoxide and further water and / or carbon dioxide and / or paraffins.

The combination of the two-step process according to the invention with a process for the catalytic conversion of oxygen-containing organic compounds to lower olefins and / or aromatic hydrocarbons can be carried out in three ways.

According to the first embodiment, the first step reaction product consisting of oxygen-containing organic compounds, hydrogen, carbon monoxide and a by-product containing carbon dioxide and / or water and / or C 1 paraffins, is split into at least two fractions, one of which is all oxygen-containing organic compounds and contains at least 50 vol.3 of the by-product and one contains all hydrogen and carbon monoxide The latter fraction may contain the remainder of the by-product »The fraction containing the oxygen-containing organic compounds is catalytically converted to lower olefins and / or aromatic 8003751 * * -16- hydrocarbons and the fraction containing hydrogen and carbon monoxide is catalytically converted in the aforementioned second step of the process of the invention In this embodiment, the reaction product from the first step is preferably split into two fractions, one of which contains all oxygen-containing organic compounds and the total supp one product and the other contains all hydrogen and carbon monoxide.

According to the second embodiment, at least all hydrogen, carbon monoxide and oxygen-containing organic compounds of the reaction product from the first step are used together as feed for the second step of the process according to the invention. Preferably, the total reaction product from the first step tce-15 is used as feed for the second step. The reaction product of the second step, which mainly consists of oxygen-containing organic compounds formed in the first step and paraffinic hydrocarbons formed in the second step, and which additionally contains, among other things, unreacted hydrogen and carbon monoxide, water and optionally carbon dioxide. used as feed for the additional process step in which catalytic conversion of the oxygen-containing organic compounds to lower olefins and / or aromatic hydrocarbons takes place. In view of the possibility that some of the C * paraffinic hydrocarbons formed in the second b step may be converted into aromatic hydrocarbons in the additional process step, which may be undesirable, the reaction product of the second step is preferably removed. C ^ + hydrocarbons before using this reaction product as feed for the additional process step.

According to the third embodiment, of the first step reaction product, at least all of the hydrogen, carbon monoxide and oxygen-containing organic compounds are contacted together in the additional process step with the catalyst which converts the oxygen-containing organic compounds to lower olefin and / or 5 aromatic hydrocarbons. Preferably, the total reaction product from the first step is used as feed for the additional process step. At least hydrogen and carbon monoxide should be used of the reaction product from the additional process step, which contains hydrogen, carbonone oxide, C 1-6 olefins, an aromatic-rich C + fraction, 10 C 4 paraffins, water and optionally cage dioxide from the first step. as feed for the second step of the method according to the invention. If desired, the total reaction product from the additional process step can be used as feed for the second step of the method according to the invention. Preferably, the olefins are removed from the reaction product of the additional process step before using this reaction product as feed for the second step of the process according to the invention.

It has been found by the Applicant that if the aforementioned zirconium, titanium or chromium-impregnated cobalt impregnation catalyst is used in the second step of the process, a mixture of heavy paraffinic hydrocarbons is obtained which is eminently suitable for hydrocracking in high yield to be converted to middle distillate. The hydrc-generating cracking operation is characterized by very low gas production and hydrogen consumption.

The invention is now illustrated by the following example.

8006751 -13-

700-3SSLD

In the study, the following catalysts were used.

Catalyst 1

Cu / ZnG / C ^ Q ^ catalyst with a Cu / Zn / Cr atocmver-5 ratio of 5: 3: 2.

Catalyst 2 7 -AljjO 2 calcined at 300 ° C.

Catalyst 3

Cu / ZnO / Al-O., Catalyst with a Cu / Zn atomic ratio V Λ 10 of 0.55.

Catalyst 4

Co / Zr / SiO 2 catalyst containing 25 wt. parts of cobalt and 0.9 gsw. parts of zircon per 100 wt. parts of silica which had been prepared by impregnating a silica support with an aqueous solution containing a cobalt and a zirconium salt, followed by drying the composition, calcining at 500 ° C and reducing at 250 ° C.

Catalyst 5

Crystalline aluminum silicate which, after calcination in air at 500C for one hour, had the following properties: a) thermally stable to a temperature of at least 300 ° C, b) an X-ray powder diffraction pattern substantially as shown in Table 3, and c) in the formula representing the composition of the silicate, expressed in moles of the oxides, was the SiO 2 / Al 2 O 2 mole. ratio more than 10.

8 C 0 6 7 5 1 -19-

Catalyst Mixture I

Physical mixture of catalyst 1 and catalyst 2 In a wt. 1: 1 ratio «

Catalyst mixture II

5 a layer of catalyst 3 and a layer of catalyst 4 in a vol. 1: 2 ratio.

Catalysts 1 and 4 and the catalyst mixtures I and II were tested for the preparation of methanol or dimethyl ether in one step and the preparation of paraffinic hydrocarbons and methanol or dimethyl ether in two steps. The test was carried out in one or two reactors of 50 ml each, which contained a fixed catalyst bed. Sr, seven experiments were performed. Experiments 1, 2 and 4 were performed in one step; 15 the other experiments in two steps. In the first step, a pressure of 60 bar was applied to all experts. In all experiments performed in two steps, the total reactant product from the first step was used as the feed for the second step.

The feed for the first step of experiment 7 was obtained from an H 2 / CO mixture with an Hp / CQ mol. ratio of 0.5. To this H 2 / C0 mixture was added so much water that after carrying out an external C0 shift over catalyst 3 a H 2 / C0 mole. ratio was reached 25 of 1.0. The CO2 formed during the CO shift (14.3 vol.S based on the gas mixture) was not separated. The CO 2 containing H 2 / CO mixture with H 2 / C0 mol. ratio of 1.0 was used as feed for the first step of experiment 7.

The results of experiments 1-7 are shown in Table D.

Using the composition of the product from the first step of expert 8 00 6 75 1 * d listed in Table D.

In the case of Experiment 3, a three step process was simulated for the conversion of an H 2 / CO mixture to aromatic hydrocarbons, lower olefins and paraffinic hydrocarbons.

5 Experiment 3

The product from the first step of experiment 7 can be separated into two fractions, i.e. a fraction A consisting of hydrogen and carbon oxide with an H 2 / CO mole. ratio of 0.38 and a fraction 3 consisting of dimethyl-10 ether, carbon dioxide and water in a volume ratio of 24.1: 70.5: 5.4. In experiment 8, both fractions were converted separately.

Fraction A was passed over catalyst mixture II at a temperature of 240 ° C, a pressure of 36 bar, a spatial throughput of 15 1000 Hl. 1 "1.hr" 1 and with the addition of 0.17 1 water per 1 catalyst per hour over catalyst mixture II. . The conversion of the H 2 / CO mixture was 37 vol. Taking into account the conversion of the H 2 / CC mixture in the first step of experiment 7, this means a total conversion of the H 2 / CO mixture of 93 wool.

Fraction 3 was passed over catalyst 5 at a temperature of 500 ° C, a pressure of 1 bar and a spatial flow rate of 1 g dimethyl ether / g catalyst / hour. The conversion of dimethyl ether was 100%. The hydrocarbon mixture formed was composed as follows: 30 wt.% Of an aromatics-rich C 2+ fraction o 60 wt.% Of an olefin fraction 10 wt. of a paraffin fraction.

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Of the experiments 1-8 described above, only the two-step experiments 3 and 5-7 as well as the three-step experiment 3 are experiments according to the invention. The one-step experiments 1, 2 and 4 are outside the scope of the invention. They are included in the patent application for comparison.

The following may be noted in the results set forth in Table D.

Experiments 1 and 2 demonstrate the one-step preparation of methanol. In experiment 1, a low conversion of the H 2 / C0 mixture is achieved (41 vol. 5). Compared to experiment 1, experiment 2 has a reduced spatial throughput speed of 4 times. As the result of experiment 2 shows, this increases the conversion of the H 2 / CO mixture (from 41 to 56 vol.fO, but the conversion achieved is still far too low for application of the process on a technical scale without recirculation. of the unreacted H 2 / CO mixture.

Experiment 3 demonstrates the preparation of methanol 20 and paraffinic hydrocarbons using the two-step process of the invention. Using the same spatial throughput as used in Experiment 2 (now based on the total catalyst volume in the first and second steps), a conversion of the H 2 / CO mixture of 94 vol. Is now achieved.

Experiment 4 demonstrates the one-step preparation of dimethyl ether. Compared with experiment 2 (one-step preparation of methanol), the conversion of the / CO 30 mixture is now higher (66 instead of 56 vol.?), But the conversion achieved is still far too low for application of the process on a technical scale without recirculation of the unreacted H 2 / CO mixture.

Experiments 5-7 demonstrate the preparation of 8006: -23-dimethyl ether and paraffinic hydrocarbons using the two-step process of the invention. Compared to Experiment 4, in Experiment 5, using the same total amount of catalyst, a conversion of the H 2 / CO mixture of 93 vol. Is achieved. Experiments 5 and 5 demonstrate the two-step process according to the invention, starting from Hg / CO mixtures with different Hg / 00 mol. ratio.

In view of the low H? / C0 mol. ratio of the product from the first step of Experiment 5 (1.0), in this experiment water is added to the feed for the second step. Experiment 7 is a variant of Experiment 5, in which the H? / C0 mixture with H2 / C0 mol. The ratio 1.0 used as feed for the first step was obtained by applying an external CO shift to an H / C0 mixture with an EL / CO mole. ratio of 0.5 d d, and wherein the CO 2 formed is not removed. As in Experiment 5, in Experiment 7, in view of the low Hg / CO, mol. ratio of the product from the first step (0.38), water added to the feed for the second step.

8 0 0 375 1

Claims (22)

Process for the preparation of oxygen-containing organic compounds and paraffinic hydrocarbons, characterized in that a mixture of carbon monoxide and hydrogen with an H 2 / CQ mol. ratio of at least 0.5 in a first step is contacted with a catalyst containing one or more metal components with catalytic activity for the conversion of an H 2 / CO mixture to oxygen-containing organic compounds and that carbon, monoxide and hydrogen are present in the reaction product from the first step, optionally together with other components of this reaction product, are contacted in a second step with a monofunctional catalyst containing one or more metal components with catalytic activity for the conversion of an H 2 / CO mixture to paraffin. Finic hydrocarbons, which metal components are selected from the group consisting of cobalt, nickel and ruthenium, with the proviso that if the feed for the second step is a Η ,, / CO mol. ratio of less than 1.5, water is added to this feed in an amount sufficient to react the H 2 / CO mole by reaction with CO. ratio to a value of at least 1.5 and that in the second step a bifunctional catalyst combination is used which, in addition to the metal components with catalytic activity, for the conversion of a 25 H2 / CO mixture into paraffinic hydrocarbons, in addition one or contains more metal components with CQ-shtft 8006751 -25 activity. 2. Process 70132ns claim 1, characterized in that an H / CO mixture is obtained which is obtained by steam gasification of a carbonaceous material at a temperature of 90 ° C-1500 ° C and a pressure of 10-100 bar. 3. Process according to claim 1 or 2, characterized in that a van van / CO mixture with an H ^ / CQ mol is started from. ratio of 0.75-2.5. 4. Process according to any one of claims 1-3, characterized in that an f ^ / CO mixture is started from, of which the Hg / CO mol. ratio is considered too low that water is added to this Hg / CO 'mixture in an amount sufficient to react the 15 Hg / CO mol by reaction with 00. ratio to the desired higher value and that by external or internal CO2 shift the H ^ / CO mol. ratio is brought to the desired higher value. A method according to claim 4, characterized in that an external CO shift is applied to the H 2 / C 0 mixture and that the reaction product is used as feed for the first step of the process without removal of formed carbon dioxide. 6. Process according to any one of claims 1-5, characterized in that in the first step of the process a catalyst is used which is able to convert an H 2 / CO mixture into mainly methanol or dimethyl ether. 7. Process according to any one of claims 1-6, characterized in that the first step of the process is carried out at a temperature of 225-325 ° C and a pressure of 50-150 bar. 8. Process according to any one of claims 1-7, characterized in that as a catalyst with activity for the conversion of an H 2 / C 0 mixture into paraffinic hydrocarbons which is present in the second stage. of the working methods is used, a catalyst is used which contains 10-40 wt. parts of cobalt and 0.25-5 wt. parts 5 zircon, titanium and chrome per 100 wt. parts of silica prepared by impregnating a silica support with one or more aqueous solutions of cobalt and zirconium, titanium or chromium followed by drying the composition, calcining at 350-700 ° C and reducing at 200-350 ° C C. 9. Process according to any one of claims 1-3, characterized in that water is added to the feed for the second step and that the second step is carried out using a fixed catalyst bed built from two or more alternating layers of successively particles of the CO2 shift catalyst and of the catalyst having activity for the conversion of an H 2 / CO mixture to paraffinic hydrocarbons. 10. A method according to any one of claims 1-9, characterized in that the second step is carried out at a temperature of 175-275 ° C and a pressure of 5-100 bar. 11. Process according to any one of claims 1-10, characterized in that the oxygen-containing organic compounds formed in the first step of the process are catalytically converted into lower olefins in an additional process step in the presence of a diluent and / or aromatic hydrocarbons. 12. Method according to claim 11, characterized in that the additional process step is carried out at a temperature of 300-600 ° C, a pressure of 1-50 bar, a -1 -1 spatial flow rate of 0.2-15 kg. .kg per hour and using a crystalline metal silicate as catalyst. 13. Process according to claim 11 or 12, with the 8006751 -27-% alkenraerk, which, in the additional process step, as catalyst in the additional process step, for the preparation of mainly aromatic hydrocarbons from the oxygen-containing organic compounds, as a catalyst. as defined above, of which silicate m is less than 200 is used. 14. Process according to claim 11 or 12, characterized in that in order to prepare substantially lower olefins from the oxygen-containing organic compounds, as a catalyst in the additional process step a type 1 silicate, as defined above, is used, of which silicate m is more than 200 and that the additional process step is carried out at a temperature of 400-600 ° C and a spatial throughput of 1-10 kg.kg.hr Process according to claim 11 or 12, characterized in that for the preparation of substantially lower ones. 1 olefins from the oxygen-containing organic compounds, as a catalyst in the additional process step a silicate 20 of the type 2 or 3, as defined above, is used and that the additional process step is carried out at a temperature of 300-500 ° C, a pressure of 1-5 bar and a spatial flow rate -1 -1 of 0.2-2 kg.kg.hr 16. Process according to any one of claims 11-15, characterized in that the reaction product of the first step, after separating a mixture of hydrogen and carbon monoxide therefrom, is used as feed for the additional process step and in that the separated raeng-30 Selection of hydrogen and carbon monoxide is used as feed for the second step of the process. 17. A method according to any one of claims 11-15, characterized in that the total reaction product from the first step is used as feed for the second step and the reaction product from the second step. , after having separated the C5 + hydrocarbons therefrom, is used as feed for the additional process step. 18. Process according to any one of claims 11-15, characterized in that the total reaction product from the first step is used as feed for the additional process step and in that the reaction product from the additional process step, after separating the olefins therefrom, is used as feed for the second step 10 of the method. 19. Process according to any one of claims 1-18, characterized in that in the second step of the process the cobalt catalyst described in claim 8 is used and in that the mixture of heavy paraffinic hydrocarbons obtained thereby is converted to middle distillate by hydrogenating cracking. > 20. Process for the preparation of oxygen-containing organic compounds and paraffinic hydrocarbons from a mixture of carbon monoxide and hydrogen, substantially as described above and in particular with reference to experiments 3 and 5-7 in the example. 21. Process for the preparation of paraffinic hydrocarbons as well as lower olefins and / or aromatic hydrocarbons from a mixture of carbon monoxide and hydrogen, substantially as described above and in particular with reference to experiment 8 in the example. 22. Paraffinic hydrocarbons and either oxygen-containing organic compounds or lower olefins and / or aromatic hydrocarbons prepared according to a process as claimed in claims 20 and 21. 8003751