EP4114810A1 - Procédé et système de production d'un composé cible - Google Patents

Procédé et système de production d'un composé cible

Info

Publication number
EP4114810A1
EP4114810A1 EP21710417.3A EP21710417A EP4114810A1 EP 4114810 A1 EP4114810 A1 EP 4114810A1 EP 21710417 A EP21710417 A EP 21710417A EP 4114810 A1 EP4114810 A1 EP 4114810A1
Authority
EP
European Patent Office
Prior art keywords
aldehyde
alcohol
extractive distillation
component mixture
mpa
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Withdrawn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
EP21710417.3A
Other languages
German (de)
English (en)
Inventor
Andreas Meiswinkel
Hans-Jörg ZANDER
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 EP4114810A1 publication Critical patent/EP4114810A1/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Withdrawn legal-status Critical Current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
    • 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
    • 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
    • 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
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C07C45/83—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by extractive distillation

Definitions

  • the present invention relates to a method for producing a target compound using an aldehyde and a corresponding plant according to the preambles of the independent claims.
  • the propanol is only used as an intermediate in the synthesis of an olefin from propanol, water is also one of the reaction products in this dehydration step, so that water does not have to be separated off beforehand .
  • the separation of propylene and water is comparatively easy.
  • the separation of components other than water is often more difficult in this context, especially if these other components have a significantly lower boiling point than the aldehyde and cannot be removed by condensation.
  • the aldehyde which is used in a corresponding process can be provided, for example, using a hydroformylation.
  • Typical hydroformylation processes on an industrial scale mostly start from a relatively pure feed stream with a high alkene content. Therefore, the mentioned lower-boiling components, for example carbon dioxide, lower-boiling hydrocarbons, in particular methane, but also unconverted carbon monoxide and hydrogen, are usually not present in significant amounts in the product stream either.
  • Novel processes for the hydroformylation of alkenes which can also process less pure and / or dilute feed streams, are known, for example, from DE 10 2019 119 543, DE 10 2019 119 562 and DE 10 2019 119 540.
  • Carbon monoxide and carbon dioxide can act as inhibitors in the hydrogenation described at the outset or can also lead to undesired by-products.
  • ODH oxidative dehydrogenation
  • the ODH also has the same chain length
  • Carboxylic acid i.e. acetic acid at ODHE, is formed as a by-product.
  • Ethylene can also be produced by the oxidative coupling of methane (OCM).
  • 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 alkenes such as ethylene and propylene.
  • Corresponding processes can be operated on the basis of methane, but also on the basis of other hydrocarbons or carbon-containing raw materials such as coal or biomass.
  • propylene propene
  • Propylene is conventionally produced by steam cracking of hydrocarbon feeds and conversion processes in the course of refinery processes . In the latter process, propylene is not necessarily formed in the desired amount and only as one of several components 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.
  • propylene gap An increasing demand for propylene is forecast 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. On the other hand, large quantities of methane are available as a potential feedstock;
  • hydroformylation (also referred to as oxo synthesis) represents a further technology which is used in particular for the production of oxo compounds of the type mentioned at the beginning.
  • Hydroformylation reacted ethylene or propylene, 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 also possible, but of less importance.
  • the hydroformylation, in which aldehydes are initially formed can be followed by a hydrogenation. This is also the case with embodiments of a method according to the invention. Alcohols formed by such a hydrogenation can then also be dehydrated to the respective alkenes.
  • the hydroformylation reaction in the process just mentioned is carried out over a typical catalyst at 1150 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 further described here, so that there are disadvantages compared to conventional processes. Because partial oxidation is used as a downstream 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.
  • US Pat. No. 6,049,011 A describes a process for the hydroformylation of ethylene in dilute streams.
  • the ethylene can in particular be formed from ethane.
  • propane can also be produced as a target product.
  • Alcohols formed can also be further dehydrated to alkenes.
  • this publication also does not disclose any further integration or advantageous solution for the separation of low-boiling compounds.
  • the object of the present invention is to provide an improved process for the preparation of target products such as alcohols or alkenes from aldehydes.
  • the present invention proposes a method for producing a target compound using an aldehyde and a corresponding plant with the respective features of the independent claims.
  • Preferred embodiments of the present invention are the subject matter of the dependent claims and the following description.
  • the aldehyde serves as the starting compound for the synthesis of the target compound, optionally via one or more intermediates.
  • the aldehyde can be provided by means of process steps which can also be part of the present invention.
  • the target compound can in particular be an alcohol which can be formed from the aldehyde, in particular by hydrogenation, but also an olefin which in turn can be prepared from such an alcohol, in particular by dehydration. In the latter case, an olefin is produced as the target product, the aldehyde being converted to the olefin via an alcohol as an intermediate product.
  • the target product is an alcohol formed from this aldehyde or a compound formed in turn from the alcohol. Therefore, if "the alcohol” is mentioned below, it is the target product or the intermediate product.
  • the aldehyde is provided in the context of the present invention in a component mixture which has lower boiling components than the aldehyde, in particular lower than 0 O.
  • an (alcohol) synthesis feed enriched in the aldehyde and depleted in the components boiling lower than the aldehyde is formed from the component mixture using an extractive distillation and is subjected to a reaction to form the alcohol as the target or intermediate product.
  • at least some of the alcohol is used to form an entrainer used in the extractive distillation.
  • the reaction to form the target product can also be one of several synthetic steps on the way to the target product.
  • the aldehyde and the alcohol are, in particular, compounds with linear carbon chains of equal chain length with terminal aldehyde or alcohol groups.
  • the chain length can be 2 to 20, in particular 2 to 10, further in particular 2, 3, 4, 5, 6 or 7.
  • the aldehyde is propanal and the alcohol is 1-propanol.
  • the target compound is a compound formed from the alcohol and not the alcohol itself, the target compound can in particular be an olefin, in particular propylene in the case just explained.
  • the invention is not restricted to this, although the following explanations relate predominantly to these compounds.
  • the corresponding process variants can also include the processing of several corresponding compounds.
  • the compounds boiling lower than the aldehyde can in particular be lighter hydrocarbons, for example methane, ethane or ethylene, and non-hydrocarbons boiling lower than the aldehyde, such as carbon dioxide, carbon monoxide and hydrogen.
  • the compounds mentioned boil lower than water in liquid form.
  • the invention comprises providing the aldehyde in a component mixture which contains the components mentioned which have a lower boiling point than the aldehyde.
  • a component mixture which contains the components mentioned which have a lower boiling point than the aldehyde.
  • the oxidative dehydrogenation and / or oxidative coupling of methane explained below, in each case followed by a hydroformylation, but also any other suitable process that provides a corresponding mixture of components can be used here.
  • the invention is thereby not limited, the present invention can, however, corresponding method steps, for example according to the already mentioned DE 10 2019 119 543,
  • DE 10 2019 119 562 and DE 10 2019 119 540 are particularly advantageously also suitable for processes in which significant amounts of the components mentioned, which boil below the aldehyde, are contained in the component mixture, for example for processes which comprise a step of the oxidative coupling of methane.
  • oxidative dehydrogenation is a method known in principle from the prior art.
  • known process concepts can be used for the oxidative dehydrogenation.
  • a method can be used in the oxidative dehydrogenation as described in Cavani et al., Catal. Today 2007, 127, 113.
  • catalysts containing V, Sr, Mo, Ni, Nb, Co, Pt and / or Ce and other metals can be used in conjunction with silicate, aluminum oxide, molecular sieve, membrane and / or monolith supports.
  • combinations and / or oxides of corresponding metals for example MoVTeNb oxides and mixed oxides of Ni with Nb, Cr and V can also be used in the context of the present invention.
  • MoVTeNb oxides and mixed oxides of Ni with Nb, Cr and V can also be used in the context of the present invention. Examples are in Melzer et al., Angew. Chem. 2016, 128, 9019, Gärtner et al., ChemCatChem 2013, 5, 3196, and Meiswinkel, Oxidative Dehydrogenation of Short Chain Paraffines ", DGMK conference report 2017-2, ISBN 978-3-941721-74-6, and various patents and patent applications of the applicant disclosed.
  • a typical by-product of the oxidative dehydrogenation is essentially the respective carboxylic acid in all process variants, i.e. in the case of the oxidative dehydrogenation of ethane, acetic acid, which may have to be separated off, but may represent a further product of value and typically in contents of a few percent (up to low double-digit percentage range). Carbon monoxide and carbon dioxide are also formed in the low percentage range.
  • a typical product mixture for the oxidative dehydrogenation of ethane has, for example, the following mixture proportions:
  • a typical product mixture of the oxidative coupling of methane has, for example, the following mixture proportions:
  • processing of other gas mixtures ie not provided by the oxidative coupling, is possible and advantageous if these gas mixtures contain one or more olefins in an appreciable content, for example more than 10, Contains 20, 30, 40 or 50 mol percent and up to 80 mol percent (as individual or sum values) and carbon monoxide in the same amount ranges.
  • olefins in an appreciable content, for example more than 10
  • the oxidative coupling of methane comprises a catalyzed gas phase reaction of methane with oxygen, in which one hydrogen atom is split off from two methane molecules. Oxygen and methane are activated on the surface of the catalyst. The resulting methyl radicals initially react to form an ethane molecule. A water molecule is also formed in the reaction. With suitable molar ratios of methane to oxygen, suitable reaction temperatures and the choice of suitable 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 in the oxidative coupling of methane typically include a temperature of 500 ° to 900 °, a pressure of 0.5 MPa to 1 MPa and high space velocities. More recent developments also 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.
  • the yields in the oxidative coupling of methane are comparatively low. Typically no more than 10% to 15% of the methane used is converted.
  • the comparatively harsh reaction conditions and temperatures required to cleave these bonds also favor the further oxidation of the methyl radicals and other intermediates to carbon monoxide and carbon dioxide.
  • the use of oxygen in particular plays a dual role here.
  • the methane conversion depends on the oxygen concentration in the mixture.
  • 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. ok
  • a gas mixture formed during the oxidative coupling of methane contains, in addition to the target compounds such as ethylene and possibly propylene, predominantly unconverted methane and carbon dioxide, Carbon monoxide and water. 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.
  • post bed cracking Such a specific steam cracking in a non-catalytic zone downstream of the catalytic zone is also referred to as "post bed cracking".
  • post-catalytic vapor splitting is also used for this in the following. If it is mentioned below that a starting gas mixture used according to the invention is formed or provided "using” or “using” an oxidative coupling of methane, this information should not be understood to mean that only the oxidative coupling itself is used in the provision got to. Rather, the provision of the starting gas mixture can also include further method steps, in particular post-catalytic steam splitting.
  • the alkene formed for example, in the oxidative dehydrogenation and / or oxidative coupling of methane with carbon monoxide and hydrogen can be subjected to hydroformylation to obtain an aldehyde.
  • Rh-based catalysts are typically 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. Reaction temperatures of 80 to 150 ° C. and appropriate catalysts are typically used for the production of propanal. 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, it being possible for the ligands to be present in excess. Further details are described in the article "Propanal” in Ullmann's Encyclopedia of Industrial Chemistry, 2012 edition. The invention is not restricted by the process conditions mentioned.
  • By-products in hydroformylation arise in particular from the hydrogenation of the alkene to the corresponding alkane, e.g. from ethylene to ethane, or the hydrogenation of the aldehyde to alcohol, i.e. from propanal to propanol.
  • propanal formed by hydroformylation can be used as the main source of 1-propanol in industry.
  • propanal is to be hydrogenated to 1-propanol.
  • the provision of the aldehyde in the component mixture can thus comprise, for example, using an oxidative dehydrogenation and / or oxidative coupling to form an alkene from an alkane, then at least part of the alkene formed in these reactions with carbon monoxide and hydrogen To subject the aldehyde to a hydroformylation, and to use at least part of a product mixture formed in the hydroformylation to form the component mixture.
  • the component mixture thus contains, in addition to products from oxidative dehydrogenation and / or oxidative coupling and hydroformylation, in particular unconverted starting materials and by-products.
  • the component mixture can contain unconverted ethane.
  • unconverted methane can be contained in the component mixture in considerable amounts.
  • the component mixture can also contain ethylene from the stream subjected to hydroformylation, which was not converted in the hydroformylation, as well as components used in the hydroformylation but not converted, such as hydrogen, carbon dioxide and / or carbon monoxide.
  • Extractive distillation is known to be a method of distillation for separating liquid mixtures using a comparatively high-boiling, in particular selective solvent, which is also referred to here as an entrainer.
  • Extractive distillation is based on the fact that the relative volatility of the components to be separated is influenced by the entrainer.
  • the relative volatility of one of the components can be increased or the activity coefficients of the components to be separated can be changed significantly in different directions. The result is a positive change in the separation factor in terms of separation technology.
  • the present invention comprises the conversion of the aldehyde formed, for example, in a flydroformylation, which is contained in the component mixture used, to a corresponding alcohol and optionally a further conversion, in particular to an alkene, if the alcohol is not the final target product.
  • the conversion of the aldehyde to the alcohol takes place in particular in the form of a catalytic flydration and a further conversion of the alcohol to the alkene in the case explained last in the form of dehydration with the formation of water.
  • the flydration of unsaturated components is a well-known and established technology for the conversion of components with a double bond into the corresponding saturated compounds. Typically, very high or complete conversions can be achieved with selectivities of well over 90%.
  • Typical catalysts for the flydrogenation of carbonyl compounds are based on Ni, as also described, for example, in the article "Flydrogenation and Dehydrogenation" in Ullmann's Encyclopedia of Industrial Chemistry, 2012 edition.
  • Noble metal catalysts can also be used especially for olefinic components.
  • Flydration is one of the standard reactions in industrial chemistry, as is also shown, for example, by M.
  • Typical temperatures are in the range from 200 to 250 ° for the dehydration of ethanol or 300 to 400 ° for the dehydration of 2-propanol or butanol. Due to the equilibrium limitation, the product stream is typically separated off (separation of the alkene product and also at least partially of the water by, for example, distillation) and the stream, which contains unconverted alcohol, is returned to the reactor inlet.
  • the present invention thus proposes, in embodiments, the coupling of an aldehyde supply process, which in particular comprises the production of the aldehyde, and (at least) a downstream hydrogenation, the alcohol product of the hydrogenation or a part thereof being used to form an entrainer for an extraction or extractive distillation of the crude aldehyde and is recycled accordingly in this way.
  • the alcohol product can also be used to form an entrainer in the extractive distillation when methods other than those described are used to provide a component mixture to be processed accordingly.
  • the use “for the formation” of an entrainer does not exclude the prior use of a corresponding alcohol for other purposes, for example as Absorbent as explained below, takes place and therefore the composition of the entrainer differs.
  • the extractive distillation can be carried out using the alcohol, which is formed in particular in the hydrogenation as an intermediate or target product, and that the remaining components are made from a product mixture of the aldehyde production process ("Crude aldehyde”) can be separated off in the extractive distillation without complex cryogenic separation steps.
  • components that do not take part in the reaction such as alkanes and carbon dioxide, but also not completely converted starting materials such as alkenes, carbon monoxide and hydrogen, can be carried along and separated off more easily.
  • the unreacted starting materials can be simply recycled in this way, for example, and used again in the reaction feed to produce the aldehyde.
  • Hydrogen which is formed or not converted in previous reaction steps can also be used for later hydrogenation steps.
  • a separation and / or enrichment of hydrogen can also take place, for example, by separation steps known per se, such as pressure swing adsorption.
  • a carboxylic acid in particular in the form of oxidative dehydrogenation with subsequent hydroformylation, in particular a carboxylic acid can be formed as a further by-product, in the case of ethane as use in the oxidative dehydrogenation in particular acetic acid.
  • These and other by-products and / or unreacted feedstocks from a process for providing the feed stream used for the hydroformylation can, together with water of reaction, comparatively easily, for example by condensation and / or water scrubbing, from a corresponding feed or product stream upstream or downstream the step in which the aldehyde is formed, in particular the hydroformylation, are at least partially separated off.
  • This dispensing with cryogenic separation is also advantageous for the reason that the component mixture containing the aldehyde does not need to be dried upstream of the separation.
  • This advantage applies in the same way to a CO 2 removal from the component mixture containing the aldehyde upstream of the separation.
  • drying and / or CO 2 removal if necessary partial, can be provided, but with regard to the extractive distillation and also the subsequent hydrogenation process, it is not absolutely necessary.
  • non-cryogenic separation denotes a separation or a separation step which is carried out at a temperature level above 0 O, in particular above ambient temperature.
  • “non-cryogenic” also means in particular that no C3 and / or C2 refrigerant has to be used, and that means at least temperatures of above ⁇ 30 ° C., in particular above ⁇ 20 ° C.
  • the aldehyde used in the context of the present invention has a relatively high vapor pressure compared to the alkenes and / or alkanes additionally contained in the component mixture, so that a simple distillation results in corresponding losses in the top product or in the distillation column very much many theoretical floors are required. In this way, the outlay on equipment and thus the costs increase significantly. In particular in the case of the lightest aldehyde propanal used in the context of the present invention, this is particularly true. It is precisely here that the high proportions of methane and / or ethane have a particularly negative effect due to the comparatively close proximity of the vapor pressures and / or boiling points.
  • this disadvantage is overcome by designing the separation as an extractive distillation using the alcohol formed in the hydrogenation as extraction or entrainer. According to the invention, only very little aldehyde is lost in the separation step, since most of the aldehyde, which otherwise remains gaseous, is dissolved in the entrainer or passes into the bottom liquid.
  • the components present in a component mixture are not infinitely miscible with one another.
  • it depends to a large extent on the set conditions whether there may be miscibility gaps with two liquid phases. This means that the choice of suitable process conditions can be severely restricted.
  • the use of light alcohols, such as propanol, i.e. an alcohol that is formed as a product or intermediate in the context of the present invention has a beneficial effect here because it can then be mixed with both water and hydrocarbons. Possible miscibility gaps are thus significantly reduced or even avoided by using the present invention.
  • the extractive distillation is carried out in such a way that at least 60%, 70%, 80%, 90%, 95%, 99% or 99.9% of the aldehyde contained in the component mixture, but possibly also contained water, is separated off in a bottom stream will, that is to say can be converted into a liquid fraction formed there, and in particular can be converted into the subsequent hydrogenation.
  • the extractive distillation is advantageously carried out in such a way that at most 40%, 30%, 20%, 10%, 5%, 1% or 0.1% of the components boiling below the aldehyde are separated off in the bottom stream, i.e. in a liquid fraction formed there be convicted.
  • the bottom stream thus advantageously consists predominantly of the aldehyde and the alcohol as entrainer and possibly water, while a corresponding overhead stream of the extractive distillation consists in particular of lower-boiling compounds than the aldehyde, which are also less soluble in the aldehyde than the aldehyde Alcohol or the entrainer, as well as any water contained.
  • water when it is present in low concentrations, has a significantly higher vapor pressure than pure water. This is due to the fact that the vapor pressure or the associated boiling temperature of the pure or at least highly concentrated water can be traced back to the strong hydrogen bonds between individual neighboring water molecules. In low concentrations only a few water molecules are adjacent to one another, so that only a few hydrogen bonds can be formed. In such a situation, the vapor pressure or the boiling temperature of the water fraction is dominated by the molecular mass, which results in a comparatively low boiling temperature or a comparatively high vapor pressure.
  • water present in the distillation feed can either be separated off preferably into the top stream or preferably into the bottom stream of the extractive distillation.
  • the present invention avoids the formation of azeotropes by the extractive distillation designed according to the invention.
  • the by-products of the oxidative dehydrogenation in the component mixture typically include unreacted alkane, carbon dioxide and carbon monoxide.
  • unreacted Methane is a main component of the component mixture (in addition to carbon dioxide and carbon monoxide).
  • Methane is a main component of the component mixture (in addition to carbon dioxide and carbon monoxide).
  • These compounds can be converted into the subsequent hydroformylation without problems.
  • Carbon monoxide can be reacted with the alkene together with additionally supplied carbon monoxide, which can come from dry reforming, for example.
  • the alkane is typically not converted in the hydroformylation.
  • the aldehydes formed in the hydroformylation are heavier compounds with a higher boiling point or a different polarity, they can, as already mentioned, be separated comparatively easily and also non-cryogenically from the remaining alkane in the extractive distillation according to the invention.
  • the conversion of the aldehyde to the alcohol by the hydrogenation is particularly advantageous because for this excess hydrogen contained in a product mixture of the hydroformylation can be used, which is already present in a feed mixture upstream of the hydroformylation and is passed through the hydroformylation can.
  • a content of hydrogen and carbon monoxide in a starting mixture of the hydroformylation can be set in the context of the present invention, in particular in a water gas shift of a basically known type.
  • hydrogen can be fed in at any suitable point, in particular upstream of the hydrogenation. In this way, hydrogen is available for this hydrogenation.
  • the feed need not take place immediately upstream of the hydrogenation; rather, hydrogen can also be fed in by process or separation steps that are present or carried out upstream of the hydrogenation.
  • an additional absorption is also provided, with an overhead gas being subjected to extractive distillation using an absorption liquid which is formed using at least part of the alcohol and a liquid fraction is obtained.
  • the liquid fraction formed in the absorption is advantageously at least partially in this embodiment of the invention used to form the entrainer for extractive distillation.
  • the alcohol is used here first as an absorption agent and then, when it is already partially loaded, as an entrainer in the extractive distillation.
  • the absorption phase and the entrainer phase have different compositions due to the loading of the alcohol in the absorption.
  • the alcohol formed during the reaction of the aldehyde can be separated off from unconverted alkane in a comparatively simple manner.
  • a recycle stream of the alkane can also be formed here non-cryogenically and, for example, returned to the oxidative dehydrogenation and / or oxidative coupling.
  • the present invention also extends to a system for producing a target compound, with respect to which reference is expressly made to the corresponding independent patent claim.
  • 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.
  • Examples 2 and 6 each serve as a comparison case of a conventional distillation without extraction and absorption.
  • the pressure is set to a pressure level of 2.0 MPa in each case.
  • the theoretical number of plates for the distillation or extractive distillation is indicated by n (stages column), while the number of plates in the absorber n (absorber) is only indicated if an absorber is also provided (Examples 4 and 8a / b / c).
  • Examples 1 and 5 each serve to define an exemplary feed stream (also referred to as a feed stream) for the other examples that follow.
  • the distillations in the examples are each characterized by the corresponding temperature levels in the sump (T Bottom), at the top condenser (T Condenser) and that of the exiting top stream (T OVHD).
  • T Feed indicates the temperature level of the fed feed stream from Example 1 or
  • the boil-up ratio describes the ratio of the boiled liquid, which is then sent back to the separation as a gas, and the liquid product stream withdrawn as the bottom product of the distillation (in each case in kg / h).
  • the value for efficiency bottom should be as close as possible to 100 wt .-%, in this case propanal is thus completely transferred into the bottom stream of the column. Accordingly, the value for Efficiency OVHD [split bottom: top in wt .-%] should be as close as possible to 0 wt .-%, i.e. in this case the top stream contains little or no more propanal.
  • Example 1 Provision of a feed stream from a hydroformylation
  • a feed stream A is fed to a hydroformylation.
  • 90% conversion of ethylene takes place there, carbon monoxide and hydrogen are converted accordingly stoichiometrically.
  • Further side reactions for example hydrogenation of ethylene to ethane and / or propanal to propanol
  • the product stream B of the hydroformylation is formed.
  • Table 1 Composition of the feed and product streams according to Example 1.
  • Example 2 Distillation without extraction and absorption (comparative case not according to the invention for Examples 3 and 4)
  • Example 4 extractive distillation with absorber
  • the product stream B from Example 1 is fed to an extractive distillation with absorber in accordance with the embodiment of the invention shown in FIG. 2 and explained in more detail below.
  • a stream C is provided as the feed stream, which can be processed further in one embodiment of the method according to the invention. This corresponds to the remaining gas phase fraction from stream B after condensation and separation of a liquid phase at 40 ⁇ .
  • Table 3 Composition of a material flow according to Example 5.
  • Example 6 Distillation without extraction and absorption (comparative case not according to the invention for Examples 7 and 8)
  • the stream C from Example 5 is fed to an extractive distillation without absorber corresponding to the embodiment of the invention shown in FIG. 1 and described in detail below.
  • Example 5 The stream C from Example 5 is fed to an extractive distillation with an absorber, corresponding to the embodiment of the invention which is shown in FIG. Among other things, the reflux of propanol (example 8a and 8c: 20 kg / h; example 8b: 15 kg / h) and the number of plates in the absorber (example 8a: 12; example 8b: 10;
  • Example 8c 20).
  • the temperature levels of the top and bottom fractions result from the other parameters.
  • the exact data and results are shown in Table 4.
  • the extractive distillation (Examples 7a and 7b) already leads to an improvement in the Efficiency OVHD value by more than a factor of 4 compared to the reference case (Example 6).
  • the additional absorption (Examples 8a, 8b and 8c) in turn lead to an almost quantitative propanal yield in the bottom stream.
  • Figure 1 shows an advantageous embodiment of a system according to the invention in a greatly simplified schematic representation.
  • Figure 2 shows a further advantageous embodiment of a system according to the invention.
  • Embodiments of the Invention The following explanations, which relate to the systems shown in the figures, apply in an analogous manner to the corresponding methods.
  • process steps that are carried out in a system component are denoted by the same reference numerals as the respective ones corresponding system component. If, for example, the description says that a material flow is fed to a system component, this is to be understood on the one hand to mean that this material flow is subjected to the corresponding process step in one embodiment of the process in this system component.
  • the plant 100 shown in FIG. 1 for the production of a target compound 6 comprises an extractive distillation column E, a Flydrier reactor F1 and a recirculation device R.
  • a component mixture 1 is fed into the extractive distillation column E and at least partially separated there, so that an (alcohol) synthesis feed 2 is formed as the bottom product and a top product 5 is formed.
  • the component mixture 1 contains, inter alia, an aldehyde, for example propanal.
  • An entrainer 4 is fed to the extractive distillation column E, which contains or essentially consists of an alcohol with the same chain length as the aldehyde in the component mixture 1, in particular 1-propanol.
  • the entrainer 4 which is fed into a head region of the extractive distillation column E, has a proportion of 1-propanol of more than 75%, 80%, 90%, 95% or 99%, for example a proportion of approx. 95% 1- Propanol.
  • the aldehyde is enriched in comparison to the component mixture 1, while other components contained in the component mixture 1 of the type explained above, for example an alkene, in particular ethylene, carbon monoxide, hydrogen and / or an alkane, in particular Ethane, in which the synthesis feed 2 leaving the extractive distillation column is depleted compared to the component mixture 1.
  • the synthesis feed 2 also contains a relatively large proportion of the entrainer 4.
  • the component mixture 1 can, depending on the configuration of a provision B of the component mixture 1, have a very high methane content (e.g.
  • oxidative coupling of methane when using an oxidative coupling of methane
  • methane when using an oxidative coupling of methane
  • This example can also contain 0.1% to 10% hydrogen, for example, and 5% to 50% propanal.
  • other highly volatile components such as carbon dioxide, carbon monoxide, propane, propylene, ethane and / or ethylene can be contained in variable amounts, but limited in their proportion to a total of less than 50%, in particular less than 30%. As already mentioned several times, these values relate to the dry (that is to say anhydrous) portion of the component mixture 1.
  • the component mixture 1 can also contain water, in particular be water-saturated.
  • the proportion for the further highly volatile components mentioned is typically up to 65% in total, in particular up to 40%.
  • the extractive distillation column E can be operated, for example, in such a way that the entrainer 4 is fed in with a mass flow which is between 10% and 50%, in particular between 15% and 30%, for example approx. 25%, of the mass flow of the component mixture 1 fed to the extractive distillation column E is equivalent to.
  • a bottom evaporator of the extractive distillation column E is operated in a temperature range between 50 ° and 300 °, in particular between 100 ° and 280 °, in particular between 150 ° and 250, for example about 170 ° to 190 °, while a corresponding top condenser is at one temperature from -30 ⁇ to 50 O, in particular between normal temperature (according to DIN 1945-1) and 45 O, but in any case in a non-cryogenic n temperature range, for example at about 20 O is operated.
  • the extractive distillation column E is advantageously operated in a pressure range between 0.5 MPa and 10 MPa, in particular between 1 MPa and 5 MPa, for example at about 1.5 MPa to 3.5 MPa.
  • the extractive distillation column E is designed in particular as a column with internals, a (theoretical or actual) number of plates in the range between 5 and 100, in particular between 10 and 50, for example 20, being advantageous.
  • the bottom stream or (alcohol) synthesis feed 2 in this example contains more than 85% of the propane contained in the distillation feed 1, while less than 15% of the propane used escape from the extractive distillation column E via the corresponding overhead stream 5.
  • the above-mentioned, volatile further components contained in the bottom stream 2 represent at most traces of impurities in the bottom stream 2. Their cumulative content is limited to the low two-digit ppm range, for example below 20 ppm.
  • the extractant 4 is essentially completely, in particular in a proportion of more than 85%, 90%, 95% or 99%, into the bottom stream, so that its proportion in the bottom stream 2 is between 20% and 90%, in particular between 30% and 70%, for example about 45% to 55%.
  • the bottom stream 2 is fed into the hydrogenation reactor H as feed 2 downstream of the extractive distillation column E.
  • hydrogen (not shown in the figures) is also fed into the hydrogenation reactor.
  • the hydrogen can be separated off, for example, from the top stream 5 of the extractive distillation column E, for example using an adsorption and / or membrane process.
  • the aldehyde (propanal) contained in the insert 2 is reacted in the hydrogenation reactor H with the hydrogen to form the corresponding alcohol (1-propanol).
  • a high to almost complete conversion of more than 85%, 90%, 95%, 99% or 99.9% is achieved with a high product selectivity of well over 90%.
  • a product stream 3 leaving the hydrogenation reactor can therefore essentially consist of the alcohol formed and possibly still small proportions of not have reacted aldehyde and hydrogen.
  • Part of the product stream 3 can be recycled as dilution stream 7 into the (alcohol) synthesis feed 2 upstream of the hydrogenation reactor H in order to enable better control of the process conditions in the hydrogenation reactor H.
  • the concentration of aldehyde to be converted can thus be adjusted and the temperatures prevailing in the reactor H can also be influenced.
  • Another part of the product flow 3 is fed to the return device R, in which the product flow 3 is divided. At least part of the alcohol contained in the product stream is returned as the entrainer 4 to the extractive distillation column E, while a further part of the product stream 3, optionally using further reactors and / or purification stages, is discharged from the plant 100 as the target compound 6.
  • Hydrogen possibly contained in product stream 3 can be returned to the extractive distillation column together with the extractant, where, as described, it is largely expelled via the overhead stream 5 formed there. Any unreacted aldehyde present in the product stream can likewise be returned to the extractive distillation column E together with the entrainer 4 and thus recycled into the feed 2 upstream of the hydrogenation reactor H.
  • the system 200 shown in FIG. 2 for producing a target connection 6 essentially corresponds in its components to the system 100 which has already been described in detail in connection with FIG. 1. Corresponding components of the system 200 are therefore denoted by the same reference numerals as those of the system 100 and are not described repeatedly for the sake of clarity.
  • the functioning of the absorber A is identical to that of the extractive distillation column E, but the operating parameters of the two differ from one another.
  • the absorber is operated with a sump temperature in the range from 20 ° to 60 °, in particular from 30 ° to 50 °, for example from about 40 °.
  • the (theoretical or actual) number of plates of the absorber can be between 5 and 30, in particular between 10 and 15, for example 12.
  • the absorbent 8 can, for example, also contain the alcohol from the product stream 3. In certain embodiments, however, it is also provided that a different absorbent 8 is used in order to minimize product loss via an overhead stream 9 of the absorber.
  • the liquid bottom stream of the absorber can be returned to the top of the extractive distillation column E together with the extractant 4 and / or a condensate stream formed in the top condenser of the extractive distillation column E.
  • the aldehyde contained in the distillation insert 1 is separated considerably more efficiently into the bottom stream of the extractive distillation column, so that the top stream 9 of the absorber contains practically no aldehyde, or the aldehyde leaving the absorber has a proportion of the in the distillation insert 1 contained aldehyde is less than 1%, 1 ° L ⁇ , 100 ppm or 10 ppm.
  • the overall yield of a method according to the invention using the system 200 is therefore particularly high without sacrificing selectivity.
  • the absorber A does not necessarily have to be placed directly on the top of the extractive distillation column E, as shown in FIG. 2, although this represents the preferred embodiment from a process-economical point of view.
  • space filling requirements for example, can also make a different arrangement necessary, which can nevertheless benefit from the advantages of this variant.
  • a condenser is arranged upstream of the extractive distillation column E of the plant 100 or 200, which is used to liquefy the majority of the aldehyde present in the distillation insert 1 and to transfer it separately into the hydrogenation reactor, so that the extractive distillation column E is smaller can be dimensioned, since then an overall smaller volume flow to the distillation insert 1 has to be processed.
  • a supply unit B is provided which supplies the aldehyde required for the hydrogenation H.
  • the supply unit B can, for example, as mentioned at the beginning, one or more reactors for the dry reforming of carbon dioxide, for the oxidative coupling of methane, for the oxidative dehydrogenation of ethane and / or for the hydroformylation of ethylene and corresponding
  • part of the overhead stream 5, 9 leaving the extractive distillation column E and / or the absorber A can be returned to one or more of the reactors of the preparation unit B, which in turn can increase the overall efficiency of the plant 100, 200.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'un composé cible (6) à l'aide d'un aldéhyde, le composé cible étant un alcool constitué d'aldéhyde ou d'un autre composé constitué au moins partiellement d'alcool, et l'aldéhyde étant présent dans un mélange (1) de composants qui a un point d'ébullition inférieur à celui de l'aldéhyde. Le mélange (1) de composants est utilisé pour produire, par distillation extractive (E), une charge (2) de synthèse (d'alcool) qui est enrichie en aldéhyde et qui est appauvrie en composants qui ont un point d'ébullition inférieur à celui de l'aldéhyde, et est ensuite mise à réagir pour former l'alcool. Au moins une partie de l'alcool est utilisée pour former un entraîneur (4) pour la distillation extractive (E). L'invention concerne également un système correspondant (100).
EP21710417.3A 2020-03-05 2021-03-03 Procédé et système de production d'un composé cible Withdrawn EP4114810A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020106009.2A DE102020106009A1 (de) 2020-03-05 2020-03-05 Verfahren und anlage zur herstellung einer zielverbindung
PCT/EP2021/055300 WO2021175908A1 (fr) 2020-03-05 2021-03-03 Procédé et système de production d'un composé cible

Publications (1)

Publication Number Publication Date
EP4114810A1 true EP4114810A1 (fr) 2023-01-11

Family

ID=74859888

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21710417.3A Withdrawn EP4114810A1 (fr) 2020-03-05 2021-03-03 Procédé et système de production d'un composé cible

Country Status (4)

Country Link
EP (1) EP4114810A1 (fr)
CN (1) CN115279719A (fr)
DE (1) DE102020106009A1 (fr)
WO (1) WO2021175908A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116212771A (zh) * 2023-03-09 2023-06-06 宁波巨化化工科技有限公司 一种可循环反应提高整体收率的液相单反应釜

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9118603D0 (en) * 1991-08-30 1991-10-16 Shell Int Research Process for the preparation of alcohols
ZA96178B (en) 1995-01-18 1997-06-30 Exxon Chemical Patents Inc Organic compounds and processes for their manufacture
US10766839B2 (en) * 2016-02-11 2020-09-08 Dow Technology Investments Llc Process for converting olefins to alcohols, ethers, or combinations thereof
DE102019119540A1 (de) 2019-07-18 2021-01-21 Linde Gmbh Verfahren und Anlage zur Herstellung einer Zielverbindung
DE102019119543A1 (de) 2019-07-18 2021-01-21 Linde Gmbh Verfahren und Anlage zur Herstellung einer Zielverbindung
DE102019119562A1 (de) 2019-07-18 2021-01-21 Linde Gmbh Verfahren und Anlage zur Herstellung einer Zielverbindung

Also Published As

Publication number Publication date
WO2021175908A1 (fr) 2021-09-10
DE102020106009A1 (de) 2021-09-09
CN115279719A (zh) 2022-11-01

Similar Documents

Publication Publication Date Title
EP1674441B1 (fr) Procédé pour l'hydroformylation d'olefines
EP1669337B1 (fr) Procédé pour la fabrication d'alcools à partir d'oléfines par hydroformylation et hydrogenation
WO2021009307A1 (fr) Procédé et installation pour la production d'un composé cible
EP2220017B1 (fr) Procédé continu en plusieurs étapes pour l'hydroformylation d'oléfines ou de mélanges oléfiniques supérieurs
WO2003078365A2 (fr) Procede d'hydroformylation des olefines
DE10009207A1 (de) Verbessertes Verfahren zur Hydroformylierung von Olefinen durch Reduzierung der Ameisensäurekonzentration
WO2021009312A1 (fr) Procédé et installation pour la production d'un composé cible
DE102014112792A1 (de) Verfahren und Anlage zur Herstellung von Olefinen aus Oxygenaten
EP1257518B1 (fr) Procede de preparation d'alcools c 9 et procede de preparation integree d'alcools c 9 et d'alcools c 10
WO2021009310A1 (fr) Procédé et installation pour la production d'un composé cible
DE102009027978A1 (de) Verfahren zur Herstellung von Decancarbonsäuren
DE102008007080A1 (de) Verfahren zur Herstellung von C9-Alkohol aus C8-Olefinen
WO2021175908A1 (fr) Procédé et système de production d'un composé cible
DE19510629A1 (de) Verfahren zur Herstellung eines Alkohols und für dieses Verfahren geeigneter Katalysatorvorläufer
DE102019213501A1 (de) Verfahren zur Herstellung von Isobutanol und/oder 1-Butanol
EP4015495A1 (fr) Procédé et installation de fabrication d'un composé cible
WO2021043560A1 (fr) Procédé de préparation d'alcools
DE102021202495A1 (de) Verfahren und anlage zur herstellung einer zielverbindung
DE102019213497A1 (de) Verfahren zur Herstellung von Aldehyden und/oder Alkoholen
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
WO2023104332A1 (fr) Procédé et installation pour la fabrication de diméthyléther
WO2023241919A1 (fr) Procédé de production de diméthyléther
EP3077356B1 (fr) Procédé de préparation d'acides caproïques isomères à partir des flux secondaires produits lors de la préparation de pentanals
DE102019213494A1 (de) Verfahren zur Herstellung von Alkenen

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: 20221005

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

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20240305