EP3999484A1 - Procédé et installation pour la production d'un composé cible - Google Patents

Procédé et installation pour la production d'un composé cible

Info

Publication number
EP3999484A1
EP3999484A1 EP20742712.1A EP20742712A EP3999484A1 EP 3999484 A1 EP3999484 A1 EP 3999484A1 EP 20742712 A EP20742712 A EP 20742712A EP 3999484 A1 EP3999484 A1 EP 3999484A1
Authority
EP
European Patent Office
Prior art keywords
gas mixture
hydrogen
carbon monoxide
methane
carbon number
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20742712.1A
Other languages
German (de)
English (en)
Inventor
Andreas Meiswinkel
Hans-Jörg ZANDER
Ernst Haidegger
Isabel KIENDL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Original Assignee
Linde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Publication of EP3999484A1 publication Critical patent/EP3999484A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process

Definitions

  • 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.
  • propylene propene
  • steam cracking steam cracking
  • propylene gap 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
  • the present invention proposes a method for
  • ODH oxidative dehydrogenation
  • PDH propane by dehydrogenation
  • This also applies to the production of propylene from ethylene by olefin metathesis. This process requires 2-butene as an additional starting material.
  • methane-to-olefin or methane-to-propylene processes in which synthesis gas is first produced from methane and the synthesis gas is then converted into olefins such as ethylene and propylene.
  • synthesis gas is first produced from methane and the synthesis gas is then converted into olefins such as ethylene and propylene.
  • 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.
  • 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.
  • Processing of other gas mixtures i.e.
  • oxidative coupling 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • downstream non-catalytic zone is also referred to as "post bed cracking".
  • 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
  • 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.
  • 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.
  • 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%.
  • the ethylene can in particular be formed from ethane.
  • the target product can also be propionic acid. Dehydration is also possible.
  • this publication also does not disclose any further integration and does not disclose any sensible use of the carbon dioxide formed.
  • hydrogen can also be converted with carbon dioxide to carbon monoxide and water (reversed water gas shift, RWGS).
  • RWGS reversed water gas shift
  • 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.
  • the feed gas temperature is approximately 220 ° C and carbon dioxide removal is typically provided.
  • 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
  • High temperature reactors used on an industrial scale operate in a range of
  • 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.
  • 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.
  • 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.
  • the present invention proposes a method for
  • 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
  • oxidative coupling can, for example, also be carried out without the presence or formation of hydrogen. As mentioned several times, it is not
  • the oxidative coupling of methane is a method known in principle from the prior art.
  • (essentially) pure methane or natural gas or gas can be used as the methane supplier for the oxidative coupling.
  • Coupling itself and higher hydrocarbons can preferably be fed into a post-catalytic steam cracking.
  • oxygen is particularly preferred. Air or oxygen-enriched air can in principle also be used, but lead to one
  • a diluting medium preferably steam, but also, for example, carbon dioxide
  • 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.
  • 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.
  • 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 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:
  • 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.
  • 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.
  • 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
  • Both the first and the second gas mixture can also
  • 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.
  • 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.
  • the formation of the second gas mixture always also includes the addition of hydrogen from a water gas shift used according to the invention.
  • the first gas mixture also contains unconverted methane and / or ethane and / or higher hydrocarbons, in particular paraffins. Hydrogen can also be included.
  • 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
  • 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.
  • Conversion steps comprising the hydroformylation and, subsequently, a hydrogenation and, if necessary, additionally a dehydration.
  • a compound with the second carbon number for example with three carbon atoms
  • an aldehyde for example propanal
  • 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
  • Rh-based catalysts have typically been used in corresponding processes, as described in the literature cited below. Older processes also use Co-based catalysts.
  • 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
  • reaction temperatures typically reaction temperatures of 80 to 150 ° C and corresponding
  • 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
  • Hydroformylation can be carried out in an aqueous medium and the recovery of the catalyst is easily possible.
  • 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.
  • 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
  • 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.
  • Carbon number remain in a corresponding residue if necessary further compounds with the second carbon number and higher-boiling compounds, if these are formed.
  • 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.
  • 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”.
  • Carbonyl compounds are based on Ni, as also for example in the article
  • Hydrogenation catalysts are used here, Ni and certain noble metals such as Pt and Pd, typically in supported form.
  • 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.
  • the hydrogenation is preferably carried out only with stoichiometric amounts of hydrogen or only a small amount
  • 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
  • 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.
  • a separation or enrichment can take place upstream of this water gas shift, as will also be explained below.
  • 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.
  • 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.
  • 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.
  • 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
  • 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
  • target components from the third gas mixture or subsequent mixtures thereof can be easily separated from the lower-boiling compounds mentioned.
  • 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.
  • the corresponding carbon dioxide is at least partially converted with methane to obtain carbon monoxide and / or hydrogen.
  • 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
  • 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.
  • Gas mixtures can be subjected to drying at a suitable point in each case.
  • 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.
  • 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
  • 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.
  • Boiling point or other polarity are formed, these can be comparatively simple and also non-cryogenic from the remaining lower-boiling ones
  • methane and ethane 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.
  • the fourth gas mixture contains in particular one or more paraffins, in a separation using at least part of the fourth
  • Carbon monoxide is enriched, the fifth gas mixture being at least partially fed to the water gas shift.
  • 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
  • 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.
  • separation can also include the formation of corresponding fractions without complete separation.
  • 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
  • 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
  • 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.
  • reforming and dehydration which may be provided to provide additional hydrogen, are endothermic reactions.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the alcohol formed in the reaction of the aldehyde can be any alcohol formed in the reaction of the aldehyde.
  • the present invention allows the use of all components of natural gas.
  • Natural gas fractions or raw gas are used, as explained above for the oxidative coupling of methane.
  • 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.
  • 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.
  • 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.
  • 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.
  • this part can be separated off and recycled downstream of the hydroformylation.
  • 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.
  • 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.
  • the first gas mixture in particular after one when the first gas mixture
  • 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.
  • 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,
  • the present invention also extends to a system for establishing a target connection, with respect to which the corresponding independent
  • the system has a
  • Reactor assembly which is set up, the first gas mixture under
  • FIG. 1 illustrates a method according to an embodiment of the invention in the form of a schematic flow chart.
  • 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.
  • 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
  • the method 100 further comprises a water gas shift, denoted here as a whole by 3.
  • a methane stream A is fed to process 100 or the oxidative coupling of methane 1.
  • a raw gas stream B can also be provided.
  • 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.
  • 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
  • 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
  • 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
  • ethane stream I can be provided.
  • propane and heavier components can also be separated from raw gas, the remainder of which is then provided as methane stream A.
  • an aftercooler 102 Downstream of the oxidative coupling 1, an aftercooler 102 is provided, downstream of which there is in turn a condensate separator 103.
  • 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.
  • 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.
  • 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 be
  • 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 is optionally dried in a dryer 107 and then fed to 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.
  • 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.
  • separation 108 Alternatives to separation 108 are explained below.
  • the propanal in a hydrogenation 109, can be converted to propanol.
  • the alcohol stream becomes a further, alternative to the separation 108 optional
  • 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.
  • 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.
  • 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
  • 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.
  • carbon dioxide is in the form of a material flow F
  • a separation 116 is provided in the embodiment illustrated here, in which a carbon monoxide containing or richer and
  • a further substream F2 formed in the separation 116 which can in particular contain methane and ethane, is fed into the oxidative coupling 1.
  • 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.
  • 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.
  • 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.
  • carbon monoxide is typically in the same order of magnitude as the olefin
  • the hydrogen content is not sufficient to
  • a targeted and needs-based setting of the ratio of hydrogen to carbon monoxide is through the use of the inventively provided
  • a corresponding supply of additional additional hydrogen can also come from other sources, e.g. by means of classic reforming or from water electrolysis.
  • 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
  • P OCM H 2
  • 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.
  • Equation VI n total (H 2 ) - n OCM (H 2 ) - n external (H 2 ) (VI)
  • n total (CO) n OCM (C 2 H 4 ) (VI II)
  • n total (H 2 ) 2 n OCM (C 2 H 4 ) (IX)
  • n OCM (C 2 H 4 ) n OCM (CO) + n OCM (H 2 ) + n external (H 2 ) + n external (CO) (X)
  • the OCM product gas ideally fulfills the following equation:
  • n OCM (C 2 H 4 ) n OCM (CO) + n OCM (H 2 ) (XI)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé (100) pour la production d'un composé cible, selon lequel un premier mélange gazeux est préparé, ledit mélange contenant au moins une oléfine ayant un premier nombre d'atomes de carbone et du monoxyde de carbone, et selon lequel un deuxième mélange gazeux, qui est formé au moyen d'au moins une partie du premier mélange gazeux et qui contient au moins l'oléfine ayant le premier nombre de carbones, de l'hydrogène et du monoxyde de carbone, est soumis à une ou plusieurs étapes de réaction en vue de l'obtention d'un troisième mélange gazeux qui contient un composé ayant un deuxième nombre de carbones et au moins du monoxyde de carbone, l'étape de réaction ou les étapes de réaction comprenant une hydroformylation (2), et le deuxième nombre de carbones étant supérieur d'une unité au premier nombre de carbones. Selon l'invention, un quatrième mélange gazeux enrichi en monoxyde de carbone et appauvri en composé ayant trois atomes de carbone par rapport au troisième mélange gazeux est formé au moyen d'au moins une partie du troisième mélange gazeux ; le monoxyde de carbone est soumis à une réaction de conversion du gaz à l'eau (3) dans au moins une partie du quatrième mélange gazeux en vue de la formation d'hydrogène et de dioxyde de carbone, et l'hydrogène formé lors de la conversion du gaz à l'eau est utilisé pour la formation du deuxième mélange gazeux. La présente invention concerne également une installation correspondante.
EP20742712.1A 2019-07-18 2020-07-16 Procédé et installation pour la production d'un composé cible Withdrawn EP3999484A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019119562.4A DE102019119562A1 (de) 2019-07-18 2019-07-18 Verfahren und Anlage zur Herstellung einer Zielverbindung
PCT/EP2020/070197 WO2021009310A1 (fr) 2019-07-18 2020-07-16 Procédé et installation pour la production d'un composé cible

Publications (1)

Publication Number Publication Date
EP3999484A1 true EP3999484A1 (fr) 2022-05-25

Family

ID=71670255

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20742712.1A Withdrawn EP3999484A1 (fr) 2019-07-18 2020-07-16 Procédé et installation pour la production d'un composé cible

Country Status (5)

Country Link
US (1) US20220259127A1 (fr)
EP (1) EP3999484A1 (fr)
CN (1) CN114401934A (fr)
DE (1) DE102019119562A1 (fr)
WO (1) WO2021009310A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102020106009A1 (de) 2020-03-05 2021-09-09 Linde Gmbh Verfahren und anlage zur herstellung einer zielverbindung
WO2023031284A1 (fr) 2021-08-31 2023-03-09 Linde Gmbh Procédé et appareil de préparation d'un composé cible
WO2023059679A1 (fr) * 2021-10-08 2023-04-13 Rohm And Haas Company Procédé de production de méthacrylate de méthyle à partir d'éthanol

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2464916A (en) * 1947-11-29 1949-03-22 Standard Oil Co Oxo process
ZA96178B (en) 1995-01-18 1997-06-30 Exxon Chemical Patents Inc Organic compounds and processes for their manufacture
US9856198B1 (en) * 2014-12-10 2018-01-02 Dp&Pl Llc Processes for making C3 products from ethylene and syngas using hydroformylation strategies
EP3478631B1 (fr) * 2016-06-30 2020-04-22 Dow Global Technologies Llc Procédé pour la conversion du méthane en propanal
WO2018013349A1 (fr) * 2016-07-13 2018-01-18 Sabic Global Technologies B.V. Procédé intégré combinant le couplage oxydatif du méthane et le reformage à sec du méthane
WO2018210782A1 (fr) * 2017-05-16 2018-11-22 Shell Internationale Research Maatschappij B.V. Couplage oxydant du méthane

Also Published As

Publication number Publication date
US20220259127A1 (en) 2022-08-18
WO2021009310A1 (fr) 2021-01-21
CN114401934A (zh) 2022-04-26
DE102019119562A1 (de) 2021-01-21

Similar Documents

Publication Publication Date Title
EP3999485A1 (fr) Procédé et installation pour la production d'un composé cible
EP3999484A1 (fr) Procédé et installation pour la production d'un composé cible
EP3999483A1 (fr) Procédé et installation pour la production d'un composé cible
EP3293171B1 (fr) Procédé pour la production flexible d'aldéhydes
EP1669337B1 (fr) Procédé pour la fabrication d'alcools à partir d'oléfines par hydroformylation et hydrogenation
EP2432772A1 (fr) Installation et procédé de production d'hydrocarbures de qualité supérieure à partir de méthane
WO2009080395A1 (fr) Procédé continu en plusieurs étapes pour l'hydroformylation d'oléfines ou de mélanges oléfiniques supérieurs
EP3080066B1 (fr) Hydroformylation en deux etapes au moyen des technologies de circulation de gaz et de phase ionique liquide supportée (silp)
DE102009027978A1 (de) Verfahren zur Herstellung von Decancarbonsäuren
DE69627133T2 (de) Hydroformylierung eines mehrkomponenteneinsatzstromes
EP1257518A1 (fr) Procede de preparation d'alcools c 9 et procede de preparation integree d'alcools c 9 et d'alcools c 10
DE102013101577B4 (de) Verfahren und Anlage zur Herstellung von Olefinen aus Oxygenaten
EP4114810A1 (fr) Procédé et système de production d'un composé cible
EP3693356A1 (fr) Production flexible de mtbe ou etbe et isononanol
DE112017005411T5 (de) Neuartige prozessintegration eines pyrolyseschritts mit methan oder höheren kohlenwasserstoffen, um ethylen und methanol und/oder wasserstoff zu erzeugen
DE102019213501A1 (de) Verfahren zur Herstellung von Isobutanol und/oder 1-Butanol
WO2022129575A1 (fr) Procédé et installation pour produire un composé cible
DD245866A1 (de) Verfahren zur herstellung von c tief 2- bis c tief 4-olefinen
WO2022096592A1 (fr) Procédé et installation pour produire un ou plusieurs hydrocarbures
DE102019213497A1 (de) Verfahren zur Herstellung von Aldehyden und/oder Alkoholen
WO2021043560A1 (fr) Procédé de préparation d'alcools
DE102020101054A1 (de) Verfahren und Anlage zur Herstellung eines oder mehrerer Olefine
WO2017207107A1 (fr) Procédé et installation de fabrication d'éthanol
WO2017207108A1 (fr) Procédé et dispositif de fabrication d'éthanol
EP2985271A1 (fr) Procédé et installation de fabrication d'oléfines

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220209

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C01B 3/16 20060101ALI20230412BHEP

Ipc: C07C 31/10 20060101ALI20230412BHEP

Ipc: C07C 29/141 20060101ALI20230412BHEP

Ipc: C07C 11/06 20060101ALI20230412BHEP

Ipc: C07C 1/24 20060101ALI20230412BHEP

Ipc: C07C 11/04 20060101ALI20230412BHEP

Ipc: C07C 2/82 20060101ALI20230412BHEP

Ipc: C07C 47/02 20060101ALI20230412BHEP

Ipc: C07C 45/50 20060101AFI20230412BHEP

INTG Intention to grant announced

Effective date: 20230504

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20230915