EP3999484A1

EP3999484A1 - Method and facility for producing a target compound

Info

Publication number: EP3999484A1
Application number: EP20742712.1A
Authority: EP
Inventors: Andreas Meiswinkel; Hans-Jörg ZANDER; Ernst Haidegger; Isabel KIENDL
Original assignee: Linde GmbH
Current assignee: Linde GmbH
Priority date: 2019-07-18
Filing date: 2020-07-16
Publication date: 2022-05-25
Also published as: WO2021009310A1; US20220259127A1; DE102019119562A1; CN114401934A

Abstract

The invention relates to a method (100) for producing a target compound, wherein a first gas mixture is provided which contains at least one olefin with a first carbon number and carbon monoxide, and a second gas mixture, which is formed using at least part of the first gas mixture and contains at least the olefin with the first carbon number, hydrogen, and carbon monoxide, is subjected to one or more reaction steps, thereby obtaining a third gas mixture, which contains a compound with a second carbon number and at least carbon monoxide. The one or more reaction steps include a hydroformylation process (2), and the second carbon number is greater than the first carbon number by one. According to the invention, a carbon monoxide-enriched fourth gas mixture is formed using at least part of the third gas mixture, said fourth gas mixture being depleted of the compound with three carbon atoms in comparison to the third gas mixture; the carbon monoxide in at least one part of the fourth gas mixture is subjected to a water-gas shift reaction (3), thereby forming hydrogen and carbon dioxide; and the hydrogen formed in the water-gas shift reaction is used in the formation of the second gas mixture. The invention likewise relates to a corresponding facility.

Description

description

Method and system for establishing a target connection

The present invention relates to a method for producing a target compound, in particular propylene, and a corresponding plant according to the preambles of the independent claims.

The project that led to the present patent application was funded under grant agreement No. 814557 of the European Union's Horizon 2020 research and innovation program.

State of the art

The production of propylene (propene) is described in the specialist literature, for example in the article "Propylene" in Ullmann's Encyclopedia of Industrial Chemistry, 2012 edition. Propylene is conventionally produced by steam cracking (Steam

Cracking) of hydrocarbon feeds and conversion processes in the course of refinery processes. In the latter process, propylene is not used

necessarily in the desired amount and only as one of several

Components formed in a mixture with other compounds. Other

Processes for the production of propylene are also known, but not in all cases, for example in terms of efficiency and yield, are satisfactory.

An increasing demand for propylene is predicted for the future ("propylene gap"), which requires the provision of corresponding selective processes. At the same time, it is important to reduce or even prevent carbon dioxide emissions. As a potential

Feedstock, on the other hand, has large quantities of methane available, which are currently only very limited for recycling and mostly incinerated.

The present invention has the object of providing a process for the production of propylene, which is improved in particular in view of these aspects, but also for the production of other organic target compounds, in particular of

Oxo compounds such as aldehydes and alcohols with a corresponding

Carbon backbone to provide. Disclosure of the invention

Against this background, the present invention proposes a method for

Production of a target compound, in particular propylene, and a corresponding system with the respective features of the independent claims.

Preferred embodiments of the present invention are the subject matter of the dependent claims and the description below.

In addition to the steam cracking processes mentioned above, there are also a large number of different processes for converting hydrocarbons and related compounds into one another, some of which are to be named below as examples.

For example, the conversion of paraffins to olefins of the same chain length by oxidative dehydrogenation (ODH, in the case of ethane also referred to as ODHE) is known. The production of propylene from propane by dehydrogenation (PDH) is also known and is a commercially available and established process. This also applies to the production of propylene from ethylene by olefin metathesis. This process requires 2-butene as an additional starting material.

Finally, there are so-called methane-to-olefin or methane-to-propylene processes (MTO, MTP), in which synthesis gas is first produced from methane and the synthesis gas is then converted into olefins such as ethylene and propylene. Corresponding processes can be based on methane, but also based on other hydrocarbons or carbonaceous

Raw materials such as coal or biomass are operated.

However, ethylene can also be produced by the oxidative coupling of methane (OCM). Since the oxidative coupling of methane is preferred

Embodiment of the present invention is used, it will first be explained in more detail below. The oxidative coupling of methane is described in the literature, for example in JD Idol et al., “Natural Gas”, in: JA Kent (ed.), “Handbook of Industrial Chemistry and Biotechnology”, Volume 2, 12th edition, Springer , New York 2012. In principle, however, also within the scope of the present invention Processing of other gas mixtures, i.e. not provided by the oxidative coupling, is possible and advantageous if these gas mixtures contain one or more olefins in an appreciable amount, for example more than 10, 20, 30, 40 or 50 mol percent and up to 80 mol percent ( as individual or sum values) and carbon monoxide in the same quantity ranges. If the present invention is described below with specific reference to the oxidative coupling of methane and ethylene which is formed in the oxidative coupling, this is not intended to imply any restriction.

According to the current state of knowledge, the oxidative coupling of methane comprises a catalyzed gas phase reaction of methane with oxygen, in the case of that of two

Methane molecules each split off one hydrogen atom. Oxygen and methane are activated on the catalyst surface. The emerging

Methyl radicals initially react to form an ethane molecule. A water molecule is also formed during the reaction. With suitable ratios of methane to oxygen, suitable reaction temperatures and the choice of suitable ones

Under catalytic conditions, the ethane is then oxydehydrogenated to ethylene, a target compound in the oxidative coupling of methane. Another water molecule is formed here. The oxygen used is typically completely converted in the reactions mentioned.

The reaction conditions for the oxidative coupling of methane typically include a temperature of 500 to 900 ° C., a pressure of 5 to 10 bar and high space velocities. More recent developments go in particular towards the use of lower temperatures. The reaction can be carried out homogeneously or heterogeneously in a fixed bed or in a fluidized bed. In the oxidative coupling of methane, higher hydrocarbons with up to six or eight carbon atoms can also be formed, but the focus is on ethane or ethylene and possibly also propane or propylene.

Especially due to the high binding energy between carbon and

Hydrogen in the methane molecule, the yields in the oxidative coupling of methane are comparatively low. Typically no more than 10 to 15% of the methane used is converted. In addition, the comparatively harsh reaction conditions and temperatures favor the cleavage of these Bonds are required, including the further oxidation of methyl radicals and other intermediates to carbon monoxide and carbon dioxide. The use of oxygen in particular plays a dual role here. So is the methane conversion from that

Oxygen concentration in the mixture depends. The formation of by-products is linked to the reaction temperature, since the total oxidation of methane, ethane and ethylene preferably takes place at high temperatures.

Although the low yields and the formation of carbon monoxide and

Carbon dioxide can partly be counteracted by the choice of optimized catalysts and adapted reaction conditions, a gas mixture formed during the oxidative coupling of methane contains mainly unconverted methane as well as carbon dioxide, carbon monoxide and water in addition to the target compounds such as ethylene and possibly propylene. Any non-catalytic cleavage reactions that may take place may also contain considerable amounts of hydrogen. In the parlance used here, such a gas mixture is also referred to as a “product mixture” of the oxidative coupling of methane, although it predominantly does not contain the desired products but also the unreacted starting material methane and the by-products just explained.

In the oxidative coupling of methane, reactors can be used in which a catalytic zone is followed by a non-catalytic zone. The gas mixture flowing out of the catalytic zone is transferred to the non-catalytic zone, where it is initially still at the comparatively high temperatures that are used in the catalytic zone. In particular, due to the presence of the water formed during the oxidative coupling of methane, the reaction conditions here are similar to those of conventional vapor cracking processes. Therefore ethane and higher paraffins can be converted into olefins here. Further paraffins can also be fed into the non-catalytic zone, so that the residual heat from the oxidative coupling of methane can be used in a particularly advantageous manner.

Such a targeted vapor splitting in one of the catalytic zones

downstream non-catalytic zone is also referred to as "post bed cracking". The term “post-catalytic vapor splitting” is also used for this in the following. Is it mentioned below that a used according to the invention Starting gas mixture is formed or provided "using" or "using" an oxidative coupling of methane, this information should not be understood in such a way that only the oxidative coupling itself has to be used in the provision. Rather, further method steps, in particular one, can also be made from the provision of the starting gas mixture

post-catalytic vapor cracking.

According to particularly preferred embodiments of the present invention, paraffins, in particular ethane, which are separated from any material streams at a suitable point or can be contained in corresponding material streams, can be recycled alone or together with other components for post-catalytic vapor splitting. The separation, if carried out, takes place at a point suitable for separation technology, that is to say at a position at which the separation is particularly inexpensive and in particular non-cryogenic. If it is mentioned below that ethane or another paraffin apart from methane is "returned" to the process, this can in particular mean a return to the post-catalytic vapor splitting. In contrast, methane that is "fed back into the process" is used in particular for the oxidative coupling of methane.

However, recycling can also take place together and in particular together with carbon monoxide in the oxidative coupling as a whole.

Hydroformylation is another technology that is used in particular for the production of oxo compounds of the type mentioned at the beginning.

Propylene is typically converted in the hydroformylation, but it is also possible to use higher hydrocarbons, in particular hydrocarbons having six to eleven carbon atoms. The conversion of hydrocarbons with four and five carbon atoms is basically also possible, but of less practical importance. The hydroformylation, in which aldehydes can initially be formed, can be followed by a hydrogenation. Alcohols formed by such a hydrogenation can then be dehydrated to the respective olefins.

In Green et al., Catal. Lett. 1992, 13, 341, a process for the production of propanal from methane and air is described. In the process presented, basically low yields based on methane are recorded. In which In the process, an oxidative coupling of methane (OCM) and a partial oxidation of methane (POX) to hydrogen and carbon monoxide are carried out, which is then followed by hydroformylation. The target product is the mentioned propanal, which has to be isolated as such. One limitation arises from the oxidative coupling of methane to ethylene, for which only lower conversions and limited selectivities are typically achieved at present. Differences in the Green et al. described method for the present invention are explained below with reference to the advantages achievable according to the invention.

The hydroformylation reaction in the process just mentioned is carried out over a typical catalyst at 115 ° and 1 bar in an organic solvent. The selectivity for the (undesired) by-product ethane is in the range from approx. 1% to 4%, whereas the selectivity for propanal should reach more than 95%, typically more than 98%. Extensive integration of

Process steps or the use of carbon dioxide, which is formed in large quantities as a by-product in the oxidative coupling of methane in particular, is not described further here, so that there are disadvantages compared to conventional processes. Because partial oxidation is used as a subsequent step for oxidative coupling in the process, i.e. there is a sequential interconnection, large amounts of unconverted methane from oxidative coupling have to be dealt with in the partial oxidation or separated in a costly manner.

No. 6,049.01 1 A describes a process for the hydroformylation of ethylene

described. The ethylene can in particular be formed from ethane. When

In addition to propanal, the target product can also be propionic acid. Dehydration is also possible. However, this publication also does not disclose any further integration and does not disclose any sensible use of the carbon dioxide formed.

In the water gas shift reaction (WGSR), carbon monoxide is reacted with water vapor to form carbon dioxide and hydrogen. It is an exothermic equilibrium reaction, with in

In the opposite direction, hydrogen can also be converted with carbon dioxide to carbon monoxide and water (reversed water gas shift, RWGS). Details can be found, for example, in the articles "Hydrogen, 2. Production" and "Synthesis Gas" in Ullmann's Encyclopedia of Industrial Chemistry. With water gas shift, a distinction is made in particular between low and high temperature processes (Low Temperature Shift, LTS, and High Temperature Shift, HTS).

For high temperature processes, in particular iron or

Chromium oxide catalysts are used, which are exposed to a feed gas at approx. 350 ° C. The temperature rises to 400 to 450 ° C. due to the exothermic nature of the shift reaction. In order to avoid excessively high outlet temperatures, the inlet temperature is limited accordingly. At

In low temperature processes, the feed gas temperature is approximately 220 ° C and carbon dioxide removal is typically provided. For

Typically, low-temperature processes use copper, zinc and aluminum mixed oxides with promoters (e.g. with traces of potassium).

A commercial catalyst for a high temperature process comprises

for example about 74.2% diiron trioxide, 10.0% dichromium trioxide, 0.2% magnesium oxide and volatile components in the remainder. The chromium oxide acts to

Stabilizes the iron oxide and prevents sintering. High temperature reactors used on an industrial scale operate in a range of

Atmospheric pressure up to approx. 8 MPa.

The typical composition of a commercial catalyst for a

Low temperature process is 32 to 33% copper oxide, 34 to 53% zinc oxide, 15 to 33% dialuminum trioxide. The active catalytic species is copper oxide and the function of zinc oxide is to prevent the poisoning of copper by sulfur. The dialuminum trioxide prevents dispersion and pellet shrinkage. The upper temperature limit for low-temperature processes results from the susceptibility of copper to thermal sintering. These lower temperatures also reduce the occurrence of side reactions.

In principle, in the context of the present invention, high and low temperature processes can be used for the water gas shift. These are also based in particular on the amount of heat available or usable.

For example, in the optionally used oxidative coupling, a large amount of heat from the product mixture formed at high temperatures can be used, for example, to preheat the insert in a high-temperature process.

Advantages of the invention

Against this background, the present invention proposes a method for

Production of a target compound, in particular of propylene, in which a first gas mixture is provided, the at least one olefin with a first

Contains carbon number and carbon monoxide. In the context of the present invention, it can be provided in particular that methane is subjected to oxidative coupling with oxygen to obtain ethylene and other components, including the carbon monoxide mentioned, but also possibly unconverted methane and ethane and carbon dioxide. The first gas mixture represents a starting mixture which is processed further within the scope of the present invention to produce the target compound. The first gas mixture can also contain water, depending on how it is provided. Hydrogen can also be contained in the first gas mixture. However, the presence of hydrogen and other components is not

Prerequisite, even if a corresponding first gas mixture should be described below as containing hydrogen or containing further components. The oxidative coupling can, for example, also be carried out without the presence or formation of hydrogen. As mentioned several times, it is not

necessarily the subject of the invention, but provided in one embodiment.

As already mentioned at the beginning, the oxidative coupling of methane is a method known in principle from the prior art. In the context of the present invention, for the oxidative coupling of methane on known

Process concepts are used.

In embodiments of the present invention, (essentially) pure methane or natural gas or gas can be used as the methane supplier for the oxidative coupling.

Accompanying gas fractions of different purification stages up to the corresponding raw gas can be used. For example, natural gas can also be fractionated, with methane being converted into the oxidative coupling if an oxidative coupling is used

Coupling itself and higher hydrocarbons can preferably be fed into a post-catalytic steam cracking. As an oxidizing agent in a corresponding Process, oxygen is particularly preferred. Air or oxygen-enriched air can in principle also be used, but lead to one

Entry of nitrogen into the system. A separation at a suitable point in the process would in turn be comparatively expensive and would have to be carried out cryogenically.

In the embodiments of the present invention in which it is used, a diluting medium, preferably steam, but also, for example, carbon dioxide, can be used in the oxidative coupling, in particular to moderate the reaction temperatures. Carbon dioxide can also (partially) serve as an oxidizing agent. In principle, compounds that are likewise suitable as diluents, such as nitrogen, argon and helium, again require expensive separation. With the current state of technology, however, recycled methane in particular serves as a diluent, which is only converted to a comparatively small proportion.

In embodiments of the present invention, the oxidative coupling can be carried out in particular at an excess pressure of 0 to 30 bar, preferably 0.5 to 5 bar, and a temperature of 500 to 1100.degree. C., preferably 550 to 950.degree. In principle, it is possible to fall back on catalysts known from the specialist literature, see, for example, Keller and Bhasin, J. Catal. 1982, 73, 9, Hinsen and Baerns, Chem. Ztg. 1983, 107, 223, Kondratenko et al., Catal. Be. Technol. 2017, 7, 366-381. Farrell et al., ACS Catalysis 6, 2016, 7, 4340, Labinger, Catal. Lett. 1, 1988, 371, and Wang et al., Catalysis Today 2017, 285, 147.

The conversion of methane in the oxidative coupling in the context of the present invention can be in particular more than 10%, preferably more than 20%, particularly preferably more than 30% and in particular up to 60% or 80%. The particular advantage of the embodiments of the present invention in which an oxidative coupling is used, however, is not primarily in the increased yield, but in the fact that, in addition to, in particular, a relatively high relative proportion of carbon monoxide in relation to ethylene in the product mixture of the oxidative coupling, that is, the first gas mixture used in the context of the present invention, can be used, and that this can be operated in a yield-optimized manner by using a water gas shift, as explained below. Typical by-products of the oxidative coupling of methane are carbon monoxide and carbon dioxide, which are formed in the low to double-digit percentage range. A typical product mixture of the oxidative coupling of methane within the meaning of the invention has, for example, the following mixture proportions:

Hydrogen 0.1 to 10 mole percent

Methane 20 to 90 mole percent

Ethane 0.5 to 30 mole percent

Ethylene 5 to 50 mole percent

Carbon monoxide 5 to 50 mole percent

Carbon dioxide 0.5 to 30 mole percent

These details relate to the dry portion of the product mixture, which can also contain water vapor in particular. Further components such as higher hydrocarbons and aromatics can be present in concentrations of typically less than 5 mol percent, in particular less than 1 mol percent, oxygenates - i.e. aldehydes, ketones, ethers, etc. - can be present in traces, i.e. typically less than 0.5 mol percent, in particular less than 0.1 mol percent in the product mixture of the oxidative coupling.

As already mentioned several times, the first gas mixture provided within the scope of the present invention can also be formed by other processes, or other processes can be involved in its formation. The composition of the gas mixture can in particular be as described above for the product mixture of the oxidative coupling, but can also deviate therefrom.

In the context of the present invention, a second gas mixture, which is formed using at least part of the first gas mixture and contains at least the olefin with the first carbon number, hydrogen and carbon monoxide, is obtained with a third gas mixture which is a compound with a second carbon number and at least Contains carbon monoxide, one or more

Reaction steps which comprise or comprise a hydroformylation are subjected. Both the first and the second gas mixture can also

Contain carbon dioxide. Carbon dioxide can be formed in particular with an oxidative coupling of methane, but it can also originate from and arise from other processes get into the first and / or second gas mixture in this way. For example, carbon dioxide is also formed in the water gas shift according to the invention. Forming the second gas mixture using at least a portion of the first

The gas mixture can in particular also include the separation of carbon dioxide from the first gas mixture or a part thereof, with the remainder being partially or completely used to form the second gas mixture. A separation of carbon dioxide can also take place further downstream at a suitable point. As explained below, the formation of the second gas mixture always also includes the addition of hydrogen from a water gas shift used according to the invention.

If the oxidative coupling is used, but also in other cases, the first gas mixture also contains unconverted methane and / or ethane and / or higher hydrocarbons, in particular paraffins. Hydrogen can also be included. In addition to the carbon monoxide, the third gas mixture can also contain other components, in particular secondary compounds that are present in one or more

Implementation steps are formed. Compounds, for example paraffins such as methane and / or ethane, can also get into the third gas mixture from the first gas mixture without conversion in the one or more conversion steps.

The second carbon number is one greater than the first due to the hydroformylation reaction that is part of the one or more reaction steps

Carbon number. If, for example, the oxidative coupling is used, the olefin with the first carbon number is ethylene and the compound with the second carbon number is in particular propanal, propanol and / or propylene.

As explained below, a total of two, three (or more)

Conversion steps can be provided, comprising the hydroformylation and, subsequently, a hydrogenation and, if necessary, additionally a dehydration. In each of these steps a compound with the second carbon number (for example with three carbon atoms) is formed, namely in the hydroformylation in the form of an aldehyde (for example propanal), in the hydrogenation in the form of an alcohol

(e.g. propanol) from the aldehyde, and in the dehydration in the form of an olefin (e.g. propylene) from the alcohol. The third gas mixture can therefore, when several conversion steps are used, a product mixture of each of these Be conversion steps, so a product mixture from the hydroformylation, a product mixture from the hydrogenation or a product mixture from the

Dehydration. It is not excluded in each case that further of the conversion steps following the formation of the third product mixture

are carried out or that only the implementation steps mentioned and not further implementation steps or other processing steps such as a

Cleaning, separation, drying or the like can be carried out.

Processes for hydroformylation are also known in principle from the prior art. Recently, Rh-based catalysts have typically been used in corresponding processes, as described in the literature cited below. Older processes also use Co-based catalysts.

For example, homogeneous, Rh (I) -based catalysts with phosphine and / or phosphite ligands can be used. These can be monodentate or bidentate complexes. Be used for the production of propanal

typically reaction temperatures of 80 to 150 ° C and corresponding

Catalysts used. All of the methods known from the prior art can also be used within the scope of the present invention.

The hydroformylation typically works with a ratio of hydrogen to carbon monoxide of 1: 1. However, this ratio can in principle be in the range from 0.5: 1 to 10: 1. The Rh-based catalysts used can have a Rh content of 0.01 to 1.00 percent by weight, the ligands being im

Excess may be present. Further details are in the article "Propanal" in

Ullmann's Encyclopedia of Industrial Chemistry, 2012 edition. The invention is not restricted by the process conditions mentioned.

In a further process, as described, for example, in the "Hydroformylation" chapter in Moulijn, Makee & van Diepen, Chemical Process Technology, 2012, 235, a pressure of 20 to 50 bar for a Rh-based catalyst and a pressure of 20 to 50 bar for a Co -based catalyst, a pressure of 70 to 200 bar is used. Co also appears to be relevant for hydroformylation in metallic form. Other metals are more or less insignificant, especially Ru, Mn and Fe. The temperature range used in the process mentioned is between 370 K and 440 K. In the process disclosed in the chapter "Synthesis involving Carbon Monoxide" in Weissermel & Arpe, Industrial Organic Chemistry 2003, 135, mainly Co- and Rh-phosphine complexes are used. With specific ligands, the

Hydroformylation can be carried out in an aqueous medium and the recovery of the catalyst is easily possible.

According to Navid et al., Appl. Catal. A 2014, 469, 357, in principle everyone can

Transition metals, which are capable of forming carbonyls, are used as potential hydroformulation catalysts, an activity according to this disclosure according to Rh> Co> Ir, Ru> Os> Pt> Pd> Fe> Ni being observed.

By-products in the hydroformylation arise in particular through the

Hydrogenation of the olefin to the corresponding paraffin, e.g. from ethylene to ethane, or the hydrogenation of the aldehyde to alcohol, i.e. from propanal to propanol. According to the article "Propanols" in Ullmann's Encyclopedia of Industrial Chemistry, 2012 edition, propanal formed by hydroformylation can be used as the main source of 1-propanol in industry. In a second step, propanal can be hydrogenated to 1-propanol.

In general, regardless of the specific type, sequence and number of the implementation steps mentioned within the scope of the present invention, at least a portion of the third gas mixture is used to form a fourth gas mixture which is depleted in the compound with the second carbon number and enriched in carbon monoxide compared to the third gas mixture. This formation of the fourth gas mixture can, in particular, result in a non-cryogenic separation of the

Include compound with the second carbon number, so that lighter-boiling compounds remain in the fourth gas mixture. Such a separation is particularly simple in the case of the production of an aldehyde or alcohol as a compound with the second carbon number because of the comparatively high boiling point. The separation of a corresponding olefin with the second carbon number, for example propylene, from lower-boiling compounds is likewise comparatively simple in terms of separation technology. Depending on the

Composition of the third gas mixture, the fourth gas mixture can therefore in particular be hydrogen, possibly carbon dioxide, methane, ethane and possibly residues of ethylene exhibit. Other lower-boiling compounds which are formed in the one or more reaction steps, for example as by-products, can also be included. In addition to connecting with the second

Carbon number remain in a corresponding residue if necessary further compounds with the second carbon number and higher-boiling compounds, if these are formed.

If it is mentioned here that liquids or gases or corresponding mixtures are rich or poor in one or more components, "rich" is intended to mean a content of at least 90%, 95%, 99%, 99.5%, 99.9 %, 99.99% or 99.999% and "poor" mean a content of no more than 10%, 5%, 1%, 0.1%, 0.01% or 0.001% on a molar, weight or volume basis. The term "predominantly" denotes a content of at least 50%, 60%, 70%, 80% or 90% or corresponds to the term "rich". Liquids and gases or corresponding mixtures can also be enriched or depleted in one or more components in the language used here, these terms referring to a corresponding content in a starting mixture. The liquid or the gas or the mixture is "enriched" if at least 1, 1-fold, 1, 5-fold, 2-fold, 5-fold, 10-fold, 100-fold or 1,000-fold content, "Depleted" if a maximum of 0.9, 0.5, 0.1, 0.01 or 0.001 times the content of a corresponding component, based on the starting mixture, is present. In this sense, a (theoretically possible) complete separation represents a depletion to zero with respect to a component in one fraction of a starting mixture, which therefore passes completely into the other fraction and is present in enriched form. This is also included in the terms "enrichment" and "depletion".

If it is said here that a separation takes place, a mere enrichment of certain material flows in corresponding components or a depletion in other components can take place at any time. All technologies known to the person skilled in the art can be used here, for example absorptive or adsorptive processes, membrane processes and enrichment or separation steps based on organometallic frameworks.

As mentioned, in embodiments of the present invention, a

Flydration and optionally a dehydration and / or further conversion steps of the components formed in the hydroformylation, here the aldehyde, for

Production of further products take place. Each of these products can have a

Represent the target compound of the method proposed according to the invention.

The hydrogenation of different unsaturated components is a well-known and established technology for the conversion of components with a

Double bond in the corresponding saturated compounds. Typically, very high or complete conversions with selectivities of well over 90% can be achieved. Typical catalysts for the hydrogenation of

Carbonyl compounds are based on Ni, as also for example in the article

"Hydrogenation and Dehydrogenation" in Ullmann's Encyclopedia of Industrial

Chemistry, 2012 edition. Noble metal catalysts can also be used especially for olefinic components. Hydrogenations belong to the standard reactions of technical chemistry, as also, for example, in M. Baerns et al., "Example 11.6.1: Hydrogenation of double bonds", Technische Chemie 2006,

439. In addition to unsaturated compounds (meaning olefins in particular), the authors also name other groups of substances, such as, for example, in particular aldehydes and ketones as substrates for a hydrogenation. Low-boiling substances such as butyraldehyde from hydroformylation are hydrogenated in the gas phase. When

Hydrogenation catalysts are used here, Ni and certain noble metals such as Pt and Pd, typically in supported form.

For example in the article "Propanols" in Ullmann's Encyclopedia of Industrial

Chemistry, 2012 edition, describes a heterogeneous gas phase process that is carried out at 110 to 1500 and a pressure of 0.14 to 1.0 MPa with a ratio of hydrogen to propanal of 20: 1. A reduction takes place with excess hydrogen and the heat of the reaction is dissipated by circulating the gas phases through external heat exchangers or by cooling the reactor inside. The efficiency based on hydrogen is more than 90%, the conversion of the aldehyde takes place up to 99.9% and it results

Alcohol yields greater than 99%. Commonly used commercial catalysts include combinations of Cu, Zn, Ni and Cr supported on alumina or kieselguhr. Dipropyl ether, ethane and propyl propionate are mentioned as typical by-products that can be formed in traces. According to the general prior art, the hydrogenation is preferably carried out only with stoichiometric amounts of hydrogen or only a small amount

Excess hydrogen.

Details for corresponding liquid phase processes are also given in the literature. These are carried out, for example, at a temperature of 95 to 1200 and a pressure of 3.5 MPa. Typically Ni, Cu, Raney Ni or supported Ni catalysts which are reinforced with Mo, Mn and Na are preferred as catalysts. For example, 1-propanol can be produced with a purity of 99.9%. The main problem with purifying 1-propanol is removing water from the product. If, as in one embodiment of the present invention, propanol is dehydrated to propylene, water is one of the factors in this step too

Are reaction products, so that no water has to be separated off beforehand. The separation of propylene and water is therefore easy.

The dehydration of alcohols over suitable catalysts to produce the corresponding olefins is also known. In particular, the production of ethylene (from ethanol) is common and gains in connection with the

increasing production quantities of (bio) ethanol in importance. The commercial application has been realized by different companies. For example, reference is made to the already mentioned article “Propanols” in Ullmann's Encyclopedia of Industrial Chemistry and Intratec Solutions, “Ethylene Production via Ethanol Dehydration”, Chemical Engineering 120, 2013, 29. The dehydration of 1- or 2-propanol to propene has so far not been of any practical value. Nevertheless, the dehydration of 2-propanol in the presence of mineral acid catalysts can be carried out very easily at room temperature or above. The reaction itself is endothermic and equilibrium limited. High conversions are favored by low pressures and high temperatures. Typically, heterogeneous catalysts based on Al ₂ O ₃ or SiO ₂ are used. In general, several types of acidic catalysts are suitable, and molecular sieves and zeolites, for example, can also be used. Typical temperatures are in the range from 200 to 250 ° C for the dehydration of ethanol or at 30 0 to 400 ° C for the

Dehydration of 2-propanol or butanol. Due to the

Equilibrium limitation, the product stream is typically separated off

(Separation of the olefin product and also at least partially of the water by, for example, distillation) and the stream, which contains unconverted alcohol, is used for Recirculated reactor inlet. This can be very high overall

Selectivities and yields can be achieved.

In the context of the present invention, carbon monoxide is subjected to a water gas shift in at least part of the fourth gas mixture with the formation of hydrogen and carbon dioxide. Here, a separation or enrichment can take place upstream of this water gas shift, as will also be explained below. According to the invention, hydrogen formed in the water gas shift is at least partly used in the formation of the second gas mixture and is thus fed to the one or at least one of the several conversion steps.

The present invention thus proposes overall (at least) the coupling of a hydroformylation process and a water gas shift, the

Hydroformylation and, if applicable, subsequent process steps are or are fed with hydrogen which is formed in the water gas shift, the water gas shift carbon monoxide being supplied from downstream of the hydroformylation, i.e. from the third or via the fourth gas mixture. One embodiment of the invention comprises the provision of the first gas mixture by means of an oxidative coupling of methane.

In the context of the present invention, particular advantages result from the fact that the water gas shift with the carbon monoxide from the third or fourth gas mixture as the starting material can provide hydrogen as required. This is a main aspect of the present invention.In the oxidative coupling of methane, in which carbon monoxide and carbon dioxide are inevitably formed as by-products, no consideration needs to be given to the formation of these components due to the divisibility of these components due to the water gas shift, but the oxidative coupling can be yield-optimized Conditions are operated. A corresponding embodiment of the present invention is therefore particularly advantageous.

In general, a particular advantage within the scope of the present invention is that components from the first or second gas mixture can be used in the hydroformylation and, if necessary, subsequent conversion steps without complex cryogenic separation steps. In particular, any paraffins that have formed and / or present and any methane present can be extracted from the first or second The gas mixture is carried along in the hydroformylation and can then be separated off more easily or hydrogen, which is optionally contained in the first or second gas mixture, can be used in addition to the hydrogen from the water gas shift for later hydrogenation steps. In this way, paraffins and methane can simply be recycled and reused in a reaction feed, as already mentioned above with reference to the oxidative coupling and the

post-catalytic vapor cracks explained. Carbon dioxide can come off the first

Gas mixture or a part thereof can be separated and obtained in any purity. As mentioned, there is also a separation further downstream, that is

for example from the second or third gas mixture or a part thereof in each case. Conversely, due to the comparatively high boiling points, target components from the third gas mixture or subsequent mixtures thereof can be easily separated from the lower-boiling compounds mentioned.

In one embodiment, the present invention can also include that the carbon dioxide, which was separated from the first gas mixture or further downstream and which had previously been formed as a by-product in the oxidative coupling, is converted in any process step, for example also a dry reforming. In the case of dry reforming, the corresponding carbon dioxide is at least partially converted with methane to obtain carbon monoxide and / or hydrogen.

By using the water gas shift, the present invention enables precise adaptation of the respective hydrogen and / or carbon monoxide contents to the respective requirement for corresponding components in the hydroformylation or subsequent process steps, such as, for example, the hydrogenation.

The present invention enables an increase in the possible yield of products of value, for example the oxidative coupling, through the use of the

Carbon monoxide as a reactant in hydroformylation and in

Water gas shift. At the same time, within the scope of the present invention, the effort involved in product purification and breakdown, in particular by avoiding cryogenic separation steps, is reduced. The separation of C2 and C3 components in particular can take place at comparatively moderate temperatures and, if necessary, avoiding drying. Overall, the energy efficiency is improved and large cycles, which are conventionally required due to the limited conversions in the oxidative coupling, are avoided or minimized. Steps that do not add value, such as methanation, are avoided within the scope of the present invention, as is the formation of by-products and by-products as in other processes for the production of target products such as propylene.

In the aforementioned article by Green et al. the synthesis of propanal from methane and air has already been described, with an overall low yield based on methane being reported. In this process, a combination of oxidative methane coupling and partial oxidation is used, followed by one

Hydroformylation. The target product is propanal, which must be isolated as such. Limitations here are the oxidative coupling of methane to ethylene, for which only low conversions and limited selectivities are achieved nowadays. A more extensive integration of process steps is in Green et al. not described. The advantages that can be achieved according to the invention are therefore not given here. One in Green et al. The scheme listed shows the partial oxidation as a downstream unit for oxidative coupling. Because of this sequential interconnection, large quantities of methane have to be dealt with in the partial oxidation, which are not converted in the oxidative coupling. The present invention overcomes corresponding disadvantages by the proposed measures.

In Green et al. A water gas shift is not mentioned at any point, but merely a return of carbon dioxide in a total recycling for partial oxidation is indicated. It is proposed that ethylene, carbon dioxide and water be cryogenically separated from a product stream so that a residue containing methane, carbon monoxide and hydrogen remains. This cannot be implemented in practice, since a cryogenic separation of carbon dioxide and / or water will result in very rapid relocation through solid carbon dioxide or ice.

In addition to the lack of information on a water gas shift, information on a corresponding carbon monoxide recycling can be found in Green et al. not either. All that is outlined is a carbon monoxide recycling via a partial oxidation in the hydroformylation inlet. As mentioned, in a method for providing the

Starting gas mixture, for example in the oxidative coupling, more

By-products are formed. If suitable, for example together with water of reaction, these can optionally be separated from a corresponding product mixture of the oxidative coupling and thus the first gas mixture by a condensation and / or water scrubbing.

Carbon dioxide can be suitable due to its high interaction with

Solvents or washing liquids can also be removed comparatively easily from the product mixture, with known methods for

Carbon dioxide removal, in particular appropriate washes (for example amine washes) can be used. A cryogenic separation is not necessary, so that the entire process of the present invention, at least including the hydroformylation, manages without cryogenic separation steps. Should subsequent steps require the absence or only a very low residual concentration of carbon dioxide (e.g. due to catalyst inhibition or poisoning), the residual carbon dioxide content after an amine wash can be further reduced by an optional caustic wash as fine cleaning, as required.

Any water-containing products obtained in the context of the present invention

Gas mixtures can be subjected to drying at a suitable point in each case. For example, drying can take place downstream of the hydroformylation if, in one embodiment of the present invention, this takes place in the aqueous phase and the hydrogenation downstream of the hydroformylation requires a dry stream as the reaction feed. If this is not necessary for the subsequent process steps, drying does not have to take place until it is completely dry, but water contents can also remain in corresponding gas mixtures, if these are tolerable. Different drying steps can also be provided at different points in the process and possibly with different degrees of drying.

The byproducts just mentioned are advantageously separated off completely non-cryogenically and are therefore extremely simple in terms of apparatus and energy consumption. This represents a significant advantage of the present invention over methods according to the prior art, which typically require laborious separation of undesired components in subsequent process steps.

A “non-cryogenic” separation should be understood to mean a separation or a separation step which is in particular at a temperature level above 0 ° C, in particular at typical cooling water temperatures of 5 to 40 ° C, in particular 5 to 25 ° C , is carried out, if necessary also above

Ambient temperature. In particular, a non-cryogenic separation in the sense understood here represents a separation without the use of a C2 and / or C3 cooling circuit and it therefore takes place above -30 ° C, in particular above -20 ° C.

If it comes from an oxidative coupling, there are typically no components in a corresponding first gas mixture in addition to the olefin

converted methane, ethane and carbon monoxide. However, corresponding components can also come from other processes, as mentioned. These compounds can be converted into the subsequent hydroformylation without problems. Paraffins such as methane and ethane are typically not converted in the hydroformylation. Since in the hydroformylation heavier compounds with higher

Boiling point or other polarity are formed, these can be comparatively simple and also non-cryogenic from the remaining lower-boiling ones

Components are separated. Instead of a complete separation, it is also possible for certain material flows to be enriched in corresponding components or in other components to be enriched. All technologies known to the person skilled in the art can be used here, for example absorptive or adsorptive processes, membrane processes and enrichment or separation steps based on organometallic frameworks. As mentioned, at least the carbon monoxide of this is converted in the water gas shift and the hydrogen formed can be fed to the hydroformylation or subsequent conversion steps such as the hydrogenation.

In particular methane and ethane, or more generally one or more paraffins, can or can be fed back into the process in embodiments of the invention, for example into the oxidative coupling that may be used at the points mentioned, or into other process steps. Ethane does not necessarily need to be in a separate reactor section can be returned for post-catalytic steam splitting, but can also be returned to the oxidative coupling as a whole without being separated from the methane. Before this, however, there is in particular a separation into a carbon monoxide fraction and a fraction that contains methane and ethane or the one or more paraffins.

In general, the fourth gas mixture contains in particular one or more paraffins, in a separation using at least part of the fourth

Gas mixture, a fifth gas mixture is formed which, compared to the fourth gas mixture, is depleted in the one or more paraffins

Carbon monoxide is enriched, the fifth gas mixture being at least partially fed to the water gas shift.

In detail, the fourth gas mixture can thus in particular contain methane and one or more further paraffins, the carbon monoxide in at least part of the fourth gas mixture being subjected to the water gas shift in that it is converted into a subsequent fraction and only this is subjected to the water gas shift. The fourth gas mixture thus contains in particular methane and one or more further paraffins, in a separation using at least part of the fourth

Gas mixture, a fifth gas mixture is formed which is depleted in methane and the at least one paraffin and enriched in carbon monoxide compared to the fourth gas mixture and the fifth gas mixture is at least partially fed to the water gas shift. As mentioned, the term “separation” can also include the formation of corresponding fractions without complete separation.

In the separation in which the fifth gas mixture is formed, a sixth gas mixture is advantageously also formed, which is enriched in the one or more paraffins and depleted in carbon monoxide compared to the fourth gas mixture, with at least a part of the sixth gas mixture in the

Provision of the first gas mixture is used. For example, this sixth gas mixture can at least partially be subjected to the oxidative coupling of methane and / or to a further method step used to provide the first gas mixture, in particular the post-catalytic vapor splitting. If such a separation is used, if the sixth gas mixture contains methane, a first fraction containing methane and a second fraction containing one or more paraffins can be formed using at least part of the sixth gas mixture, the first fraction at least partially the oxidative coupling of methane and the second fraction is at least partially subjected to a post-catalytic vapor cracking step downstream of the oxidative coupling of methane. The appropriate fractions are each

advantageously essentially free of the other compounds.

In a particularly advantageous development, the present invention can include energy integration, that is to say a coupling of heat flows for endothermic and exothermic reactions. Exothermic reactions are in particular the oxidative coupling, if used, and the hydroformylation. The water gas shift is also an exothermic reaction. On the other hand, reforming and dehydration, which may be provided to provide additional hydrogen, are endothermic reactions. In the present invention, in which an oxidative coupling is carried out, the use of the waste heat from this appears to be of particular advantage for other processes, since these are at a comparatively high level

Temperature level of typically more than 800 ° C takes place.

In the context of the present invention, the aldehyde formed in the hydroformylation can be the target compound, or in the context of the present invention this aldehyde can be converted further into an actually desired target compound. The latter variant in particular represents a particularly preferred embodiment of the present invention.

In particular, during the conversion of the aldehyde to the target compound, the aldehyde can first be hydrogenated to an alcohol which has a carbon chain with the second carbon number, that is to say the same carbon number as the aldehyde. A corresponding process variant is particularly advantageous because it can use hydrogen formed in the process itself, which is already present in a feed mixture upstream of the hydroformylation and can be passed through the hydroformylation. In the process according to the invention and its embodiments, hydrogen can be fed in at any suitable point, in particular upstream of the optionally provided hydrogenation. In this way, hydrogen is available for this hydrogenation. The feed does not have to take place immediately upstream of the hydrogenation; Rather, hydrogen can also by upstream of the

Hydrogenation present or carried out process or separation steps are fed. Hydrogen can, for example, already be contained in the first gas mixture, and at least part of this hydrogen can be used in the hydrogenation. Furthermore, hydrogen can also be separated from a partial flow of a product flow of the water gas shift or formed as a corresponding partial flow, for example by separation steps known per se, such as pressure swing adsorption.

According to a further embodiment of the present invention, during the conversion of the aldehyde to the actual target compound of the process according to the invention, the alcohol formed by the hydrogenation is dehydrated to a further olefin (based on the earlier olefin contained in the starting gas mixture), the further olefin, in particular Propylene, one

Carbon chain with the mentioned second carbon number, ie the carbon number of the previously formed aldehyde and of the alcohol formed therefrom.

In particular, the alcohol formed in the reaction of the aldehyde can

can be separated comparatively easily from unreacted paraffin. In this way, a return flow of the paraffin can also be formed here non-cryogenically and, for example, returned to the oxidative coupling.

In a particularly preferred embodiment, the present invention allows the use of all components of natural gas. Any

Natural gas fractions or raw gas are used, as explained above for the oxidative coupling of methane. Thus, using natural gas, a methane-containing natural gas fraction and an ethane-containing natural gas fraction can be formed, the methane-containing natural gas fraction being subjected to the oxidative coupling of methane and the ethane-containing natural gas fraction preferably being subjected to the post-catalytic steam cracking step. Further aspects of the present invention have also already been mentioned in principle. In particular, the carbon dioxide can at least partially be separated non-cryogenically from the first gas mixture or downstream thereof and used in some other way and, for example, purified. The carbon monoxide and the olefin in the remainder of the starting gas mixture and, if appropriate, further components in this, can at least in part be subjected to the hydroformylation without prior separation from one another. More generally speaking, the olefin with the first carbon number and the carbon monoxide from the first gas mixture can therefore be subjected to the hydroformylation in the second gas mixture at least partially unseparated from one another. As mentioned, a complete non-cryogenic separation of gas mixtures obtained can in principle be achieved within the scope of the present invention. This does not necessarily apply to the aforementioned separation of natural gas into the methane fraction and the fraction with heavier hydrocarbons.

As already mentioned, the starting gas mixture can in particular contain methane and a paraffin, with at least some of the methane and the paraffin being able to pass through the hydroformylation unconverted. As mentioned in detail above, this part can be separated off and recycled downstream of the hydroformylation. Depending on the expediency, the separation can take place directly downstream of the hydroformylation, i.e. before each process step following the hydroformylation, or downstream of a process step following the hydroformylation, for example after a hydrogenation or dehydration, but also after any separation or processing steps.

In the context of the present invention, as already mentioned, an amount of hydrogen formed in the water gas shift can be adapted to a hydrogen requirement in the hydroformylation and / or hydrogenation. This is precisely where a particular advantage of the present invention lies.

In a particularly preferred embodiment of the present invention, the first gas mixture, in particular after one when the first

Gas mixture taking place condensate separation is compressed to a pressure level at which the hydroformylation is carried out and optionally the carbon dioxide is separated off. Between the possibly provided separation of carbon dioxide and the Hydroformylation can also be provided with additional intermediate steps. In one embodiment of the present invention, the water gas shift is carried out at a lower pressure level, so that the pressure level of the hydroformylation and possibly the carbon dioxide removal represents the highest of the pressure levels. In this way, further compression can be dispensed with. The first gas mixture is provided if oxidative coupling is used,

advantageously at the pressure level specified above for the oxidative coupling of methane and the hydroformylation is advantageously carried out at a pressure level of 15 to 100 bar, in particular 20 to 50 bar.

The present invention also extends to a system for establishing a target connection, with respect to which the corresponding independent

Claim is expressly referenced. A corresponding system, which is preferably set up to carry out a method, as previously explained in different configurations, benefits in the same way from the advantages already mentioned above.

In a particularly preferred embodiment, the system has a

Reactor assembly, which is set up, the first gas mixture under

Use of an oxidative coupling of methane to provide.

The invention is first explained in more detail below with reference to the accompanying drawing, which illustrates a preferred embodiment of the present invention. An exemplary embodiment of the invention will then be explained in more detail, which is carried out in particular using the method illustrated in the drawing.

Brief description of the drawings

FIG. 1 illustrates a method according to an embodiment of the invention in the form of a schematic flow chart.

If process steps such as the oxidative coupling of methane, water gas shift or hydroformylation are mentioned below, this should also include the apparatus used for these process steps (in particular reactors, columns, washing devices, etc.), even if they are not is expressly referred to. In general, the explanations relating to the method apply in the same way to a corresponding installation.

The invention is described below using the example of oxidative coupling for providing the first gas mixture. This requires a separation of carbon dioxide. As mentioned several times, the invention is not limited to this.

Detailed description of the drawings

In FIG. 1, a method according to a particularly preferred embodiment of the present invention is illustrated in the form of a schematic flow chart and is designated as a whole by 100.

Central method steps or components of method 100 are an oxidative coupling of methane, denoted here as a whole by 1, as well as a

Flydroformylation, denoted overall by 2 here. The method 100 further comprises a water gas shift, denoted here as a whole by 3.

In the example shown, a methane stream A is fed to process 100 or the oxidative coupling of methane 1. Instead of the methane stream A or in addition to this, however, a raw gas stream B can also be provided. The

If necessary, raw gas stream B can be processed by means of any processing steps 101. A correspondingly provided feed stream is labeled E for the sake of better distinguishability. Furthermore, in the example illustrated here, the water gas shift 3 provides a steam stream B1 and (optionally) a stream B2 containing water and / or carbon monoxide from an external source.

The feed stream E, together with a substream, denoted here by F3, of a recycle stream F (or, as explained below, optionally also together with a recycle stream F2 having further components) is the oxidative

Coupling 1 supplied. Mixing with oxygen, which is provided in the form of a material flow C, and optionally with steam, which is provided in the form of a

Material flow G is provided, made. The vapor of the material flow G serves, as well as nitrogen of an optionally provided nitrogen flow H as

Diluent or moderator and in this way prevents in particular one thermal runaway in the oxidative coupling 1. Water can also make a contribution to ensuring the catalyst stability (long-term performance) and / or enabling the catalyst selectivity to be moderated.

A reactor used in the oxidative coupling 1 can provide an area for

Have implementation of a post-catalytic vapor splitting, as explained at the beginning. A partial stream F4 of the recycle stream F containing ethane can optionally be fed into this area. Alternatively or additionally there is also one

A separately provided ethane stream I can be fed in. Also one

In principle, supply of propane can be provided. The ethane stream I and possibly propane and heavier components can also be separated from raw gas, the remainder of which is then provided as methane stream A.

Downstream of the oxidative coupling 1, an aftercooler 102 is provided, downstream of which there is in turn a condensate separator 103. An Indian

Condensate stream K formed from condensate separation 103, which predominantly or exclusively contains water and possibly further, heavier compounds, can be fed to a device 104 in which in particular a (purified) water stream M and a residual stream N can be formed.

The product mixture of the oxidative coupling 1 freed from condensate, which is generally referred to here as the first gas mixture, is in the form of a stream L with a stream V from the water gas shift 3, which is rich in hydrogen and carbon dioxide and optionally carbon monoxide and not converted in the water gas shift / or contains water and possibly other components, and combined and then compressed in a compressor 105 and then fed to a total of 106 denoted carbon dioxide removal, which can be carried out, for example, using appropriate washes. In the embodiment shown here, a wash column 106a for an amine wash and the

Regeneration column 106b for the amine-containing washing liquid loaded with carbon dioxide in washing column 106a is shown. Furthermore, an optional

Washing column 106c for fine cleaning, for example for washing with lye, is shown. As mentioned, the removal of carbon dioxide through appropriate washes is basically known. It is therefore not explained separately. A carbon dioxide stream O formed in the carbon dioxide removal unit 106 can

can be used in particular in purified form for any purpose. It is particularly suitable for subsequent use in further processing, since it has a comparatively high concentration of carbon dioxide and a high degree of purity.

A component mixture remaining after the removal of carbon dioxide in the carbon dioxide removal unit 106, which is in the form of a material flow P and is generally referred to here as the second gas mixture, contains predominantly ethylene,

Ethane, hydrogen and carbon monoxide. It is optionally dried in a dryer 107 and then fed to the hydroformylation 2.

In the hydroformylation 2, propanal is formed from the olefins and the carbon monoxide, which propanal is carried out together with the further components explained in the form of a stream Q from the hydroformylation 2. In particular, unconverted ethane and other light compounds such as methane and carbon monoxide can optionally be separated off from material flow Q in a separation 108, and these can be transferred to recycle flow F. Alternatives to separation 108 are explained below.

In a hydrogenation 109, the propanal can be converted to propanol. The alcohol stream becomes a further, alternative to the separation 108 optional

provided separation 1 10 supplied, where lower-boiling components can also be separated and transferred to the recycle stream F.

The hydrogenation 109 can be operated with hydrogen, which is contained in a product stream of the water gas shift 3 and which is carried along in the hydroformylation. Alternatively, the required hydrogen can also be fed in separately in the form of a stream R, in particular from a separation of hydrogen in a pressure swing adsorption 11-1.

A product stream from the hydrogenation 109 or the optionally provided separation 110 is fed to a dehydration 112. In this propylene is formed from the propanol. A product stream S from the dehydration 1 12 is fed to a condensate separation 1 13 and there condensable compounds, especially water. The water can be carried out of the process in the form of a water stream T. The water flows N and T can, if necessary after a suitable treatment, also be fed back to the steam generation process. In this way, for example, at least part of the steam flow B1 can be provided.

The gaseous residue remaining after the condensate separation 1 13 is fed to a further separation 1 14, optionally provided as an alternative to the separations 108 and 110, where in particular also unconverted ethane and light

Compounds can be separated and transferred into the recycle stream F. A product stream U formed in the separation 114 can be carried out from the process and further process steps can be used, for example for the production of plastics or other further compounds, as indicated here overall with 115. Corresponding processes are known per se and include the use of propylene from process 100 as an intermediate product or starting product in the petrochemical value chain.

Unreacted ethane and other light compounds like methane and

As mentioned several times, carbon dioxide is in the form of a material flow F

returned. For this purpose, a separation 116 is provided in the embodiment illustrated here, in which a carbon monoxide containing or richer and

is formed in particular on other components poor or free partial flow F1. Carbon monoxide in this stream can be converted in the water gas shift 3 with the formation of further hydrogen. The resulting stream V is fed in, as described above, at a suitable point before the hydroformylation.

A further substream F2 formed in the separation 116, which can in particular contain methane and ethane, is fed into the oxidative coupling 1. In this case, a separation 1 17 can optionally be provided in which the partial flows F3 and F4 can be formed, which have already been explained above. In particular, methane and ethane can be separated from one another in this way, the methane in substream F3 in oxidative coupling 1 being able to be fed to the reactor inlet and the ethane in substream F4 being able to be fed to a reactor zone used for post-catalytic steam splitting. In principle, however, it is also possible to feed the stream F2 to the reactor inlet without separation 117. Embodiment

In the context of the present invention, a starting gas mixture was considered as it can in principle be provided by means of the oxidative coupling of methane, but which can also come from other sources. According to the invention, carbon monoxide is typically in the same order of magnitude as the olefin

(e.g. ethylene) or even in a stoichiometric excess. According to the invention, however, the hydrogen content is not sufficient to

To cover stoichiometric demand for the hydroformylation and any subsequent further reaction - as in the case of a hydrogenation described here.

For an ideal overall reaction of the integrated process proposed according to one embodiment of the present invention downstream of the provision of the starting gas mixture (hydroformylation, hydrogenation and dehydration), the following gross equation results:

C ₂ H ₄ + 2 H ₂ + CO C ₃ H ₆ + H ₂ O (I)

A targeted and needs-based setting of the ratio of hydrogen to carbon monoxide is through the use of the inventively provided

Water gas shift possible according to:

CO + H ₂ OH ₂ + CO ₂ (II)

Other versions of the oxidative coupling can in particular also lead to a low or very low hydrogen content in the product gas of the oxidative coupling. Correspondingly, there can also be a corresponding disparity in another gas mixture. Here, too, within the scope of the present invention, the additional provision of hydrogen is on the one hand by the above-mentioned

Water gas shift reaction possible. A corresponding supply of additional additional hydrogen can also come from other sources, e.g. by means of classic reforming or from water electrolysis.

In the following, a calculation example based on oxidative coupling is given to demonstrate the advantages that can be achieved according to the present invention which in particular the necessary or advantageous component proportions for a starting gas mixture are determined.

For an ideal overall reaction of the integrated process after the oxidative coupling (hydroformylation, hydrogenation and dehydration), the gross equation I.

The demand for carbon monoxide n _total (CO) and the demand for hydrogen n _total (H ₂ ) in the hydroformylation and hydrogenation reaction cascade are 1 mol of carbon monoxide per 1 mol of ethylene and 2 mol of hydrogen per 1 mol of ethylene. The amount of ethylene in the product stream of the oxidative coupling is n _OCM (C ₂ H ₄ ), the amount of

Carbon monoxide n _OCM (CO) and the amount of hydrogen P _OCM (H ₂ ).

After the oxidative coupling, the process gas preferably contains a high proportion of carbon monoxide and a certain proportion of hydrogen. If the ratio of carbon monoxide to hydrogen is set according to the stoichiometric requirement of equation I by a shift reaction according to equation II above, the amount of hydrogen n _shift (H ₂ ) is formed and at the same time the same amount of carbon monoxide n _shift (CO) consumed: n _Shift (H ₂ ) = n _Shift (CO) (I II)

Any additional CO and H ₂ demand that may be required is optionally covered by an external source, such as a reforming system. The amount of substance from this external source is n _external (H ₂ ) for hydrogen and n _external (CO) for carbon monoxide.

So CO and hydrogen demand of the gross equation I are covered as follows: n _total (CO) n _OCM (CO) - n _shift (CO) + n _external (CO) (IV) n _total (H ₂ ) = n _OCM (H ₂ ) + n _Shift (H ₂ ) + n _external (H ₂ ) (V)

The following amount of hydrogen must therefore be provided in the shift reaction: n _shift (H ₂ ) = n _total (H ₂ ) - n _OCM (H ₂ ) - n _external (H ₂ ) (VI) Substituting Equation VI into Equation IV, taking into account

Equation III gives the CO demand n _total (CO) as follows: n _total (CO) = _OCM (CO) [n _total (H ₂ ) - _OCM (H ₂ ) - n _external (H ₂ )] + n _external (CO) (VI I)

According to the stoichiometry of the gross equation I, under ideal conditions: n _total (CO) = n _OCM (C ₂ H ₄ ) (VI II) n _total (H ₂ ) = 2 n _OCM (C ₂ H ₄ ) (IX)

Inserting equations VIII and IX into equation VII results after rearranging:

3 n _OCM (C ₂ H ₄ ) = n _OCM (CO) + n _OCM (H ₂ ) + n _external (H ₂ ) + n _external (CO) (X)

In order to avoid an external supply of CO and / or H ₂ (n _external (H ₂ ) = n _external (CO) = 0), the OCM product gas ideally fulfills the following equation:

3 n _OCM (C ₂ H ₄ ) = n _OCM (CO) + n _OCM (H ₂ ) (XI)

The shift reaction according to equation II ensures the needs-based ratio between CO and H ₂ .

An import of CO and / or H ₂ is therefore necessary if:

3 n _OCM (C ₂ H ₄ )> n _OCM (CO) + n _OCM (H ₂ ) (XII)

On the other hand, there is an excess of CO and / or H ₂ if:

3 n _OCM (C ₂ H ₄ ) <n _OCM (CO) + n _OCM (H ₂ ) (XI II)

These considerations are based on idealized assumptions, but can help to derive a preferred range for gas compositions. As a result of the integration of the water gas shift provided according to one embodiment of the invention, the ratio of carbon monoxide and hydrogen can be flexibly adjusted as required.

Claims

1. A method (100) for producing a target compound, in which a first

Gas mixture is provided, the at least one olefin with a first

Contains carbon number and carbon monoxide, in which a second gas mixture that is formed using at least a portion of the first gas mixture and at least the olefin with the first carbon number, hydrogen and

Contains carbon monoxide to obtain a third gas mixture, the one

Compound having a second carbon number and containing at least carbon monoxide, is subjected to one or more reaction steps, wherein the one or more reaction steps comprises or comprise a hydroformylation (2), and wherein the second carbon number is one greater than the first carbon number, characterized in that, that, using at least a portion of the third gas mixture, a compound with the second carbon number is depleted in relation to the third gas mixture

Carbon monoxide-enriched fourth gas mixture is formed, that the carbon monoxide in at least part of the fourth gas mixture is subjected to a water gas shift (3) with the formation of hydrogen and carbon dioxide, and that the hydrogen formed in the water gas shift is at least partially used to form the second gas mixture.

2. The method according to claim 1, wherein the first gas mixture is provided using an oxidative coupling of methane (1) and at least ethylene as the olefin with the first carbon number and additionally at least methane, ethane and carbon dioxide, the carbon dioxide remaining the second gas mixture is at least partially separated from the first gas mixture or a part thereof.

3. The method of claim 1, wherein the fourth gas mixture contains one or more paraffins, wherein in a separation (1 16) using at least a portion of the fourth gas mixture, a fifth gas mixture is formed, which compared to the fourth gas mixture at the one or the several paraffins is depleted and enriched in carbon monoxide, the fifth being

Gas mixture is at least partially fed to the water gas shift (3).

4. The method of claim 3, wherein in the separation (1 16) in which the fifth gas mixture is formed, a sixth gas mixture is also formed which is enriched in relation to the fourth gas mixture to the one or more paraffins and depleted in carbon monoxide, wherein at least part of the sixth gas mixture is used in the preparation of the first gas mixture.

5. The method (100) according to any one of the preceding claims, wherein the

Reaction steps in addition to the hydroformylation (2) include one or more further reaction steps in which the one or more compounds with the second carbon number include an aldehyde formed in the hydroformylation (2) and one or more others in the one or more further subsequent steps formed connections include.

6. The method (100) according to claim 5, in which the formation of the fourth gas mixture is carried out downstream of the one or more further subsequent steps.

7. The method (100) according to claim 5 or 6, wherein the one or more further subsequent steps comprise or comprise a hydrogenation in which the aldehyde is reacted with hydrogen to form an alcohol.

8. The method (100) according to claim 7, in which the first gas mixture contains hydrogen and in which at least some of this hydrogen is used in the hydrogenation.

9. The method (100) according to any one of claims 5 to 8, wherein the one or the

several subsequent steps a dehydration, in which the alcohol is converted to an olefin, comprises or comprise.

10. The method (100) according to any one of claims 5 to 9, wherein one in the

Water gas shift (3) the amount of hydrogen formed is adapted to a hydrogen requirement in the hydroformylation and / or hydrogenation.

1 1. The method (100) according to any one of the preceding claims, wherein the olefin with the first carbon number and the carbon monoxide from the first gas mixture are fed at least partially unseparated from one another in the second gas mixture to the hydroformylation (2).

12. The method (100) according to any one of the preceding claims, wherein the first

Gas mixture is compressed to a first pressure level at which the

Hydroformylation (2) is carried out at a second pressure level, and in which the water gas shift (3) is carried out at a third pressure level, the second pressure level being the highest of the pressure levels.

13. The method (100) according to any one of the preceding claims, downstream of the

Provision of the starting gas mixture and the water gas shift (3) is carried out completely non-cryogenically.

14. Plant for the production of a target compound, which is set up to provide a first gas mixture containing at least one olefin with a first

Contains carbon number and carbon monoxide, a second gas mixture which is formed using at least a portion of the first gas mixture and at least the olefin having the first carbon number, hydrogen and

Contains carbon monoxide to obtain a third gas mixture, the one

Compound having a second carbon number and at least carbon monoxide contains, subject to one or more reaction steps, wherein the one or more reaction steps comprises or comprise a hydroformylation (2), and wherein the second carbon number is one greater than the first carbon number, characterized by means which are set up to use at least a portion of the third gas mixture to form a fourth gas mixture that is depleted in the compound with the second carbon number and enriched in carbon monoxide, the carbon monoxide in at least a portion of the fourth gas mixture to form hydrogen and To subject carbon dioxide to a water gas shift (3) and to use the hydrogen formed in the water gas shift at least in part in the formation of the second gas mixture.

15. Plant according to claim 14, which has a reactor arrangement for

is set up, the first gas mixture using an oxidative

To provide coupling of methane (1).