EP4025550A1 - Verfahren zur herstellung von alkoholen - Google Patents
Verfahren zur herstellung von alkoholenInfo
- Publication number
- EP4025550A1 EP4025550A1 EP20757309.8A EP20757309A EP4025550A1 EP 4025550 A1 EP4025550 A1 EP 4025550A1 EP 20757309 A EP20757309 A EP 20757309A EP 4025550 A1 EP4025550 A1 EP 4025550A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alcohols
- alkenes
- mixture
- hydration
- alkanes
- 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.)
- Pending
Links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
- C07C27/04—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds
- C07C27/06—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds by hydrogenation of oxides of carbon
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- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
- C07C27/04—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds
- C07C27/06—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds by hydrogenation of oxides of carbon
- C07C27/08—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds by hydrogenation of oxides of carbon with moving catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
- B01D3/145—One step being separation by permeation
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- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/36—Azeotropic distillation
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- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/40—Extractive distillation
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1418—Recovery of products
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- B01D61/362—Pervaporation
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- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
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- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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- C07C7/06—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by azeotropic distillation
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- C07C7/00—Purification; Separation; Use of additives
- C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
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- C—CHEMISTRY; METALLURGY
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Definitions
- the present invention relates to a process for the preparation of alcohols having at least two carbon atoms by catalytic conversion of synthesis gas to a mixture containing alkenes, alcohols and alkanes, alkenes contained in this mixture being converted to alcohols in at least one subsequent step.
- EP 0 021 241 B1 discloses a process for the preparation of mixtures of acetic acid, acetaldehyde, ethanol and alkenes with two to four carbon atoms by converting synthesis gas containing carbon monoxide and hydrogen in the gas phase over supported catalysts, the catalysts being rhodium and 0.1 contain up to 5.0% by weight of sodium or potassium.
- the oxygen-containing compounds and the alkenes are formed in a molar ratio of 1: 1 to 2.5: 1.
- the selectivity of the catalysts used for the alcohols is comparatively poor.
- US Pat. No. 6,982,355 B2 describes an integrated Fischer-Tropsch synthesis for the production of linear and branched alcohols and alkenes, in which a light fraction and a heavy fraction are first separated from one another and the light fraction is contacted with a dehydration catalyst to obtain a light fraction , which contains alkenes and alkanes, this is then further divided into fractions containing C5 - C9 and C10 - C13 alkenes and alkanes, which are then partially converted with synthesis gas to the aldehydes with the corresponding chain lengths. From the aldehydes contained in the alkane fraction, the corresponding alcohols, which are still contained in the alkane fraction, are then produced by reaction with hydrogen.
- these alcohols are separated from the alkanes and in a further distillation the C5 - C9 fraction and the C10 - C13 fraction become the individual ones Alcohols obtained.
- the alkanes of the appropriate fractions can be dehydrogenated to the alkenes.
- the catalysts used in the Fischer-Tropsch synthesis are cobalt, iron, ruthenium or other transition metals from group VIIIB, optionally on an oxidic carrier such as silicon dioxide, aluminum oxide or titanium oxide.
- CN108067235A describes catalysts for the production of alkenes from synthesis gas which contain cobalt and cobalt carbide as the active component, lithium as an additive and one or more other metals selected from manganese, zinc, chromium and gallium.
- higher alcohols are also formed during the conversion.
- the selectivity for a mixture of alkene should be up to 40% and that for a mixture of alcohols should be 30%.
- Straight-chain alkenes with 2 to 30 carbon atoms and primary alcohols with corresponding chain lengths are obtained.
- the product mixture mainly contains alkanes and alkenes and, depending on the catalyst, about 20% to 25% alcohols, with methanol, alcohols with 2 to 5 carbon atoms and higher alcohols with 6 or more carbon atoms being formed, the latter group of alcohols being formed make up the majority and are usually more than 50% formed.
- the publication does not contain any details on the separation of the various products contained in the mixture.
- CN108014816A describes catalysts for the conversion of carbon monoxide with hydrogen to produce mixed primary alcohols and alkenes.
- Catalysts based on cobalt, in particular dicobalt carbide and manganese on an activated carbon carrier, are used, which can contain additions of cerium, copper, zinc or lanthanum.
- Primary alcohols and alkenes with 2 to 30 carbon atoms are formed.
- the catalysts used here are said to have a high selectivity for alkenes, it being mentioned that alkenes formed can be further converted to alcohols by hydroformylation.
- No. 8,129,436 B2 describes a method for producing an alcohol mixture from synthesis gas, a mixture of alcohols and oxygen-containing compounds being obtained. It is proposed to strip the product mixture with a methanol-containing stream in order to remove a portion of the carbon dioxide and inert gases contained in the product stream. In addition, dehydration can take place downstream in order to convert some of the ethanol formed and, if appropriate, propanol into the corresponding alkenes to convert. Potassium-modified molybdenum sulfide catalysts are used to convert the synthesis gas.
- US 2010/0005709 A1 describes alternative fuel compositions which contain ethanol, isopropanol and butanols, with synthesis gas first being converted into a C2-C4 alkene stream by a Fischer-Tropsch synthesis and then these alkenes being hydrated.
- the alcohols obtained can be mixed with gasoline to obtain fuel compositions.
- the synthesis gas described in this document only about 39% hydrocarbons with 2 to 4 carbon atoms are obtained, while about 40% higher hydrocarbons, cycloalkanes and aromatic compounds with C5 to C20 are formed, as they are usually contained in gasoline or diesel.
- the object of the present invention is to develop an improved process for the production of alcohols with at least two carbon atoms by catalytic conversion of synthesis gas, in which the complex product mixture of alcohols, alkenes and alkanes can be specifically converted into secondary products and thus a high quality one Product / high quality products can be manufactured for the fuel market and / or the chemical industry. It is a further object of the present invention to provide a method of the aforementioned type in which the purification of the complex product mixture is facilitated.
- the aforementioned object is achieved by a process for the preparation of alcohols with at least two carbon atoms of the type mentioned at the beginning with the features of claim 1.
- the alkenes are converted to alcohols in at least one subsequent step by hydration of the alkenes.
- the two-stage synthesis according to the invention has an advantage in the higher alcohol yields.
- the synthesis of the higher alcohols usually gives a mixture of primary alcohols.
- secondary alcohols can be formed selectively, thus expanding the product range.
- a more uniform product is created from the complex product mixture, which leads to advantages in the purification process and in marketing logistics.
- the consecutive conversion of the alkenes, which are also initially obtained, to alcohols also has the advantage that the separation of the alkanes and alkenes, which is demanding due to the similar physical properties, can be omitted and the alkanes can be separated more easily from the product mixture.
- the hydration of alkenes to the corresponding alcohols is a known reaction for the preparation of alcohols and is used industrially, for example for the production of isopropanol from propene. With the exception of ethene, the hydration of the linear alkenes predominantly leads to the formation of secondary alcohols. Isobutene is hydrated to tertiary butanol, a tertiary alcohol.
- the alkene In direct hydration, the alkene is reacted with water over an acidic catalyst to form the respective alcohol.
- the hydration of the alkenes to alcohols is an equilibrium reaction. High pressures and low temperatures shift the equilibrium of the exothermic reaction on the product side in favor of the alcohols.
- the indirect hydration of the alkene takes place in a two-stage reaction. The alkene is first reacted with sulfuric acid to form mono- and dialkyl sulfates and then hydrolyzed to form alcohol.
- Industrially, ethanol is mainly produced by fermenting carbohydrates, for example sugars from corn, sugar beet, grain or wheat. Synthetic ethanol can be made from ethene through direct hydration.
- the direct hydration of ethene takes place in the gas phase on “solid” phosphoric acid (SPA catalysts), for example at 250-300 ° C and 50-80 bar.
- SPA catalysts solid phosphoric acid
- the hydration of ethene is an equilibrium reaction, with high pressures and low temperatures favoring the exothermic formation of the ethanol. Indirect hydration of ethene is no longer carried out industrially.
- 2-Butanol (secondary butyl alcohol) can be produced from butene or the MTBE raffinate by means of direct hydration or indirect hydration. 2-Butanol is used to manufacture methyl ethyl ketone (MEK).
- MEK methyl ethyl ketone
- synthesis gas can be provided by cleaning and conditioning various gas flows that arise in a steelworks.
- the process described in the present invention for the catalytic synthesis of alcohols having at least two carbon atoms, which are also referred to in the present application by the term “higher alcohols”, is suitable, for example, for converting synthesis gas from such sources.
- any other suitable synthesis gas sources can also be used for the process according to the invention.
- the alkanes and alkenes are first separated from the alcohols from the first mixture of alkanes, alkenes and alcohols obtained after the catalytic conversion of synthesis gas and preferably after separation of the unconverted synthesis gas and only then are the alkenes in hydrated this second mixture.
- the alcohols can be separated from the alkenes and alkanes with little effort.
- the alkenes can only be separated from the alkanes with considerable effort.
- the consecutive hydration of the alkenes to alcohols thus facilitates the separation process of alkenes and alkanes.
- the second mixture of alkanes and alkenes is first separated into two or more fractions with different numbers of carbon atoms and only then are the individual fractions hydrated separately from one another in order to obtain the to obtain corresponding alcohols.
- the separation of the alkene / alkane mixture into the individual Cx cuts or alkenes can be advantageous, since this enables the individual alkenes to be hydrated separately.
- Alkenes, the respective hydration products of which are particularly suitable for the fuel market, or alkenes which can be hydrated under mild reaction conditions or inexpensively, can be converted selectively to the respective alcohols.
- Alkenes for which there is a corresponding alkene market can be separated from the respective C-cut and marketed.
- the reaction conditions for the hydration of the individual Cx cuts or alkenes can be selected independently of one another.
- hydration of the C2 cut or of the ethene could be dispensed with and the ethene could instead be used for other applications in the chemical industry.
- a relatively pure alkane stream can be obtained in this way, which can be used for the generation of synthesis gas or energy.
- a separate system for hydrating the alkenes is required for each C cut, or the various fractions must be hydrated in batches.
- the second mixture comprising the alkanes and alkenes contains a mixture of C2-C4 or a mixture of C2-C5 alkenes, which is then hydrated as a mixture to give the corresponding alcohols.
- the hydration of an alkane / alkene mixture thus takes place without a previous separation of this mixture into different fractions with different numbers of carbon atoms being provided.
- reaction conditions for the hydration of such an alkene / alkane mixture it must be taken into account that the conventional industrial processes are optimized for the conversion of the individual alkenes and differ from one another in the choice of the catalyst and the reaction conditions.
- this step of hydrating the alkene / alkane mixture in this variant of the invention it is therefore preferable to use process conditions which enable the conversion of all alkenes or promote the conversion of the preferred alkenes to the respective alcohols.
- the hydration of the alkene mixture has the advantage that only one plant is required for hydration or that intermittent hydration of the various fractions can be dispensed with.
- the alkanes are separated from the alcohols formed.
- the alkane stream remaining after the alcohols have been separated off can then be used, for example, to generate synthesis gas or energy.
- the conditions for the hydration of the alkane / alkene mixture with regard to the selection of the catalyst and the reaction conditions, in particular the temperature and the pressure at which the hydration reaction takes place, are chosen so that the hydration of propene and / or 1-butene is favored over that of ethene. It was found that with the catalysts which were used in the context of the present invention in the production of higher alcohols by catalytic conversion of synthesis gas, propene is predominantly formed as alkene. The CO selectivity of the Conversion of the synthesis gas to the alkenes decreases in the order 1-propene>1-butene> ethene.
- the direct hydration is carried out at elevated temperatures and at elevated pressure.
- elevated temperatures and at elevated pressure In principle, wide temperature ranges and wide pressure ranges are possible here, depending on which other conditions are selected.
- the hydration takes place in the presence of an acid which acts as a catalyst.
- the alkenes can be hydrated at temperatures above 80.degree. C., in particular above 100.degree. C., for example at temperatures in the range from 100.degree. C. to 180.degree. C., preferably at 120 to 150.degree. C. and / or at a Pressure from 5 bar to 150 bar, in particular at a pressure from 10 bar to 100 bar, preferably at a pressure from 50 bar to 100 bar, for example at a pressure from 70 bar to 80 bar.
- the hydration of propene and 1-butene proceed under similar reaction conditions, for example at the aforementioned temperatures and pressures. In the industrial direct hydration of propene, conversions of for example up to about 75% per pass are achieved.
- the invention therefore proposes that the hydration reaction conditions for propene and 1-butene be based.
- a third possible preferred variant of the process according to the invention provides that the alkenes are hydrated with the mixture of alkanes, alkenes and alcohols without the alcohols having to be separated off from this mixture beforehand.
- the hydration of the alkenes in the mixture of alcohols, alkenes and alkanes obtained in the reaction of the synthesis gas, without prior separation of the alcohols contained in this mixture can, for example, offer the advantage that the reaction mixture is already at a comparatively high pressure of, for example, about 60 bar is present and therefore only needs to be preheated to the reaction temperature.
- hydration of the alkenes to give the alcohols is thermodynamically preferred.
- an elevated temperature for example up to 150 ° C
- an elevated pressure for example 2 bar to 100 bar
- a conversion of the alkenes and the primary C 3+ alcohols to the secondary alcohols takes place.
- propene and 1-butanol are mainly converted to isopropanol and 2-butanol.
- Ethene is hydrated to ethanol.
- the alkanes are separated off from the product mixture obtained after hydration and the remaining mixture of alcohols is optionally purified and / or separated into individual fractions of alcohols or individual alcohols.
- At least one step is provided in which the product mixture obtained in this reaction is separated into a gas phase and a liquid phase, with the liquid phase is used for the subsequent hydration of the alkenes to the alcohols.
- the gas phase separated off at this point can contain, for example, unconverted CO and H 2 and also C0 2 , CH 4 and N 2 .
- the gas phase obtained in this separation process which generally contains the unconverted gases mentioned, can be at least partially returned to the step of catalytic conversion of the synthesis gas, in order in this way to reactivate the recycled reactant gases to higher alcohols to increase the yield of the entire process.
- the alkenes can in principle also be hydrated before the product mixture obtained after the reaction of the synthesis gas is separated into a gas phase and a liquid phase.
- the hydration takes place, for example, directly in a reactor downstream of the synthesis of higher alcohols and without prior separation of the product mixture.
- propene and butene can be hydrated at about 150 ° C., while higher temperatures are used for the hydration of ethene for example about 230 ° C to 260 ° C are advantageous.
- the hydration can take place at a lower temperature than the previous reaction of the synthesis gas, it being possible to choose temperatures of, for example, 120 ° C. to 150 ° C. for the hydration. It can therefore be advantageous to cool the product mixture for the hydration to temperatures of this order of magnitude.
- hydration of the alkenes to give the alcohols is thermodynamically preferred.
- Tests in the context of the synthesis of the higher alcohols with specific catalysts and calculations or simulations of the subsequent hydration for an equilibrium reactor clearly show that when the hydration is carried out at, for example, about 50 ° C and a pressure of about 60 bar, a conversion of the alkenes and the primary Alcohols to the secondary alcohols takes place.
- propene and 1-butanol are predominantly converted to isopropanol and 2-butanol.
- Ethene is hydrated to ethanol.
- one of the above-mentioned variants is to be preferred, in which the separation into a gas phase and a liquid phase initially takes place after the synthesis of higher alcohols, the product mixture being cooled after the synthesis of higher alcohols from the synthesis gas.
- the method preferably comprises the steps: Production of higher alcohols (with at least two carbon atoms) and of alkenes by catalytic conversion of synthesis gas;
- the method preferably comprises the steps:
- the method preferably comprises the steps:
- a fourth variant of the process is possible in which the alkenes are hydrated after the synthesis gas has been converted and before the product mixture obtained is separated into a gas phase and a liquid phase.
- the method preferably comprises the steps:
- the combination of the two process variants can, for example, promote the isomerization of the primary alcohols to secondary alcohols.
- the isomerization of the primary alcohols to the secondary alcohols proceeds via the dehydration of the primary alcohols to the corresponding alkenes as intermediates.
- the dehydration proceeds preferably at higher temperatures than the hydration.
- the provision of the synthesis gas for the inventive catalytic conversion to alcohols can include not only the preparation of the synthesis gas but also the purification and conditioning of the synthesis gas.
- the hydrogen is preferably produced in a sustainable manner by means of renewable energies and / or low C0 2 emissions, for example by means of water electrolysis or methane pyrolysis.
- the electricity for the operation of the hydrogen generation is preferably generated by means of renewable energies.
- the catalytic synthesis of the higher alcohols from synthesis gas can be carried out according to the invention, for example, at reaction temperatures from 200 ° C to 360 ° C, preferably at temperatures from 220 ° C to 340 ° C, more preferably at 240 ° C to 320 ° C, in particular at 260 ° C to 300 ° C, for example at about 280 ° C.
- this reaction can be carried out, for example, at a reaction pressure of 10 bar to 110 bar, in particular at 30 bar to 90 bar, preferably at 50 bar to 70 bar, for example at about 60 bar.
- the product mixture obtained from unconverted synthesis gas, alcohols, alkenes and alkanes can be heated to lower temperatures of, for example, 150 ° C or less, in particular to below 130 ° C, preferably to below 110 ° C or to even lower temperatures of less than 80 ° C, for example about 40 ° C to 20 ° C, especially cooled to about 30 ° C and separated into a gas and a liquid phase.
- the gas phase mainly contains the unconverted synthesis gas as well as any inert components (eg nitrogen) and the methane formed as a by-product.
- the gas phase is usually returned to the synthesis of the higher alcohols. If necessary, a purification or conditioning of the gas phase, such as, for example, the conversion of the methane formed as a by-product into synthesis gas, is provided.
- the liquid phase mainly contains the alcohols, alkenes and alkanes formed.
- the alkenes and Alkanes are evaporated and separated from the product mixture.
- Other methods known to the person skilled in the art for separating the alkenes and alkanes from the alcohols are, however, likewise suitable here.
- the alkanes can also be dehydrated to the corresponding alkenes and then likewise hydrated in order to increase the yield of alcohols.
- the alcohols remain in the liquid phase and, after the water formed as a by-product has been separated off, are marketed as a product mixture, e.g. as a fuel additive, or separated into the individual alcohols in a distillation.
- the various options for integrating the consecutive conversion of the alkenes to alcohols in the process concept for the synthesis of the higher alcohols differ in the composition of the reaction mixture and the prevailing process conditions, such as temperature and pressure, as well as in the type and time of the separation of the alcohols, alkenes and alkanes from the synthesis gas.
- Primary alcohols are preferably formed in the catalytic synthesis of the higher alcohols from synthesis gas.
- the formation of the secondary alcohols is hardly observed.
- the hydration of the linear alkenes leads to the formation of secondary ones Alcohols such as isopropanol and 2-butanol (with the exception of ethanol).
- the synthesis of higher alcohols and the consecutive hydration of the alkenes thus differ in their product range.
- the alcohols can be separated off from the hydrocarbon mixture (alkenes, alkanes), that is to say process variants 1 and 2 mentioned above are preferred for the hydration.
- the alcohols can be separated from the alkenes and alkanes with little effort.
- the alkenes can only be separated from the alkanes with considerable effort. The consecutive hydration of the alkenes to alcohols thus facilitates the separation process of alkenes and alkanes.
- the product mixture can be processed, which comprises at least the following steps:
- Separation of the gases not absorbed in the absorption medium as a gas phase Separating an aqueous phase from the organic phase of the absorption medium, preferably by decanting; optionally distilling out the alcohols from the aqueous phase;
- the separation of the alcohols from the alkenes and alkanes or the separation of the alcohols from the alkanes before or after the hydration of the alkenes can comprise at least the following steps:
- a catalyst is used here; which comprises grains of non-graphitic carbon with cobalt nanoparticles dispersed therein, the cobalt nanoparticles having a mean diameter d p in the range from 1 nm to 20 nm and the mean distance D between individual cobalt nanoparticles in the grains of non-graphitic Carbon is in the range of 2 nm and 150 nm and w, the combined total mass fraction of the metal in the grains of non-graphitic carbon, in the range of 30% to 70% by weight of the total mass of the grains of non-graphitic Carbon, where d p , D and w satisfy the following relationship: 4.5 dp / w>D> 0.25 dp / w.
- a catalyst material which is doped with a metal selected from Mn, Cu or a mixture of these, the grains of non-graphitic carbon having a molar ratio of cobalt to doped metal in the range from 2 to 15 exhibit.
- the aforementioned grains of non-graphitic carbon with cobalt nanoparticles dispersed therein can be obtained from aqueous solutions of metallic precursors and organic carbon sources by combined spray-drying or freeze-drying of the aqueous solution and thermal treatment of the intermediate product obtained in this way at moderate temperatures.
- Non-graphitic carbon can be identified by a person skilled in the art by TEM analysis (PW Albers, Neutron Scattering study of the terminating protons in the basic structural units of non-graphitizing and graphitizing carbons, Carbon 109 (2016), 239 - 245, page 241 , figure 1c).
- the abovementioned catalysts surprisingly have a significantly higher selectivity for alkenes than for alkanes (for example in the order of about 3: 1).
- other alcohols thus fall in the product mixture Products of value that can be used advantageously materially and not energetically from an economic and ecological point of view.
- An important aspect in connection with an advantageous development of the invention is the separation of the products of value from the relatively complex product mixture at the reactor outlet.
- residual gases depending on the feed gas: H 2 , CO, C0 2 , N 2
- by-products especially alkanes, C0 2 and H 2 0
- FIG. 1 shows a graph of the temperature dependency of the equilibrium of the hydration of ethene to ethanol at a pressure of 60 bar;
- FIG. 2 shows a graph of the temperature dependence of the equilibrium of hydration from propene to propanol at a pressure of 60 bar;
- FIG. 3 shows a graph of the temperature dependence of the equilibrium of hydration of butene to butanol at a pressure of 60 bar;
- FIG. 4 shows a graphic representation of an exemplary product distribution after the catalytic conversion of synthesis gas to higher alcohols and the following
- FIG. 5 shows a graphic representation of an exemplary product distribution after the catalytic conversion of synthesis gas to higher alcohols and the following
- Hydration of the product mixture consisting of the alcohols, alkenes, alkanes and synthesis gas at a temperature of 50 ° C. and a pressure of 60 bar;
- FIG. 6 shows a graphic representation of an exemplary product distribution after the catalytic conversion of synthesis gas to higher alcohols and the following
- Hydration of the product mixture consisting of the alcohols, alkenes, alkanes and synthesis gas at a temperature of 130 ° C. and a pressure of 60 bar;
- FIG. 7 shows a graphic representation of an exemplary product distribution after the catalytic conversion of synthesis gas to higher alcohols and the following
- FIGS. 1 to 3 Dehydration of the product mixture consisting of the alcohols, alkenes, alkanes and synthesis gas at a temperature of 280 ° C and a pressure of 60 bar.
- FIGS. 1 to 3 the temperature dependency of the thermodynamic equilibrium is explained in more detail on the basis of these representations.
- FIG. 1 the temperature dependence of the equilibrium of ethene and ethanol at a pressure of 60 bar is shown graphically, in FIG. 2 the temperature dependence of the equilibrium of propene and propanol at a pressure of 60 bar and in FIG. 3 the temperature dependence of the equilibrium of butene and butanol at a pressure of 60 bar.
- Figures 1 to 3 show that under the reaction conditions of 150 ° C.
- thermodynamic equilibrium for all three reactions is on the side of the alcohols.
- the unconverted alkenes can be converted into synthesis gas together with the alkanes, for example, and fed back into the process. Because of the alkene / alkane mixture, indirect hydration of the alkenes may be preferred.
- FIG. 2 also shows that 2-propanol is formed practically exclusively, while the amount of 1-propanol is negligibly small.
- the reaction mixture consisting of alcohols, alkenes and alkanes was hydrated at a temperature of 150.degree.
- the mixture of alkenes and primary alcohols is almost completely converted into secondary alcohols under these reaction conditions.
- the isomerization of the primary alcohols into the secondary alcohols presumably takes place via the formation of the alkenes as intermediates.
- the hydration of the product mixture in the synthesis of higher alcohols from alcohols and alkenes thus offers the possibility of shifting the product spectrum in the direction of secondary alcohols.
- the industrial hydration of propene and 1-butene takes place at reaction temperatures of 120 to 150.degree.
- FIGS. 5 and 6 Using these two diagrams, the respective product distribution after the catalytic synthesis of higher alcohols according to the invention and the directly following step of the Hydration of the alkenes explained, the hydration being carried out in the two exemplary embodiments at different temperatures.
- hydration was simulated at a temperature of 50.degree. This temperature is thermodynamically preferred, as can be shown on the basis of simulations and calculations. With this purely thermodynamic consideration, however, it should be noted that the industrial processes for hydration usually take place at reaction temperatures of 130-260 ° C. It can therefore be assumed that the reaction takes place at 50 ° C. with a significantly lower reaction rate.
- the product distribution in FIG. 5 shows that after the first reaction step, the synthesis of the higher alcohols, predominantly ethanol and 1-butanol are formed on alcohols and predominantly 1-propene and 1-butene as well as some ethene and 1-pentene on alkenes.
- the main products are ethanol, 2-propanol and 2-butanol, while alkenes are only present in smaller amounts, primarily butene and some pentene.
- the hydration of the product mixture in the synthesis of higher alcohols from alcohols and alkenes thus offers the basic possibility of shifting the product spectrum in the direction of secondary alcohols.
- the industrial hydration of propene and 1-butene takes place at reaction temperatures of 120 to 150 ° C.
- FIG. 6 a diagram similar to that in FIG. 5 shows the respective product distribution after the synthesis of higher alcohols on the one hand and after the subsequent hydration, but here at a higher temperature of 130 ° C. during the hydration.
- the product distribution of the alcohols and alkenes after the first synthesis step is the same as in FIG. 5.
- thermodynamic equilibrium at 130 ° C shows that propene and pentene are partially converted to the corresponding secondary alcohols.
- ethanol and 1-butanol are dehydrated to the respective alkenes.
- 1-Propanol and 1-butanol are also partially isomerized to 2-propanol and 2-butanol. The isomerization of the linear alcohols into the secondary alcohols takes place via the formation of the alkenes as intermediate products.
- this variant depending on the reaction conditions, product composition and the reaction conditions, can be advantageous for the hydration of individual alkenes and the yield of these alcohols can be increased.
- this variant can lead to the alcohol yield being reduced and the alcohols being preferably converted into alkenes.
- a shift in the product range can be achieved.
- the product mixture obtained in this way can be converted to alcohols in a further hydration reaction, for example by combining process variant 4 with one of process variant 1, 2 or 3.
- reaction conditions for the hydration of ethene and propene are similar to the synthesis of the higher alcohols, so that, according to an alternative variant of the invention, it may be useful to hydrate the alkenes directly in a reactor downstream of the catalytic synthesis of higher alcohols and without prior separation of the Carry out product mixture. It is advantageous here that the reaction mixture is already present in the alcohol synthesis at a similar temperature and pressure level as is required for the conversion in the hydration. The reaction mixture does not have to be cooled to a low temperature and a low pressure (e.g. 30 ° C, 1 bar) and let down, but can be converted directly.
- a low temperature and a low pressure e.g. 30 ° C, 1 bar
- alkenes are preferably formed in some cases.
- an exemplary product composition is given, which was obtained in the catalytic conversion of synthesis gas according to the method according to the invention using a catalyst which comprises grains of non-graphitic carbon with cobalt nanoparticles dispersed therein, the cobalt nanoparticles a mean diameter d p in the range of 1 nm to 20 nm and the mean distance D between individual cobalt nanoparticles in the grains of non-graphitic carbon in the range of 2 nm and 150 nm and w, the combined total mass fraction of the metal in the grains of non-graphitic carbon, ranges from 30% by weight to 70% by weight of the total mass of the grains of non-graphitic carbon, where d p , D and oo satisfy the following relationship: 4.5 dp / oo >D> 0.25 dp / oo.
- the catalyst used had a high C2-C4 selectivity, with alcohols, alkenes and alkanes being formed.
- the CO selectivity for the conversion to alcohols is about 28%
- the CO selectivity for the conversion to alkenes is about 32%.
- the exact CO selectivities of the catalytic conversion of the synthesis gas result from the following table 1.
- the selectivities given in table 1 were based on the products detected in the catalytic tests (C1-C5-alcohols, C1-C5-alkenes and C1-C5- Alkanes, C02) standardized.
- the analysis of the CO conversion suggests that, in addition to the detected products mentioned, long-chain C6 + alcohols, C6 + alkenes and C6 + alkanes and, if appropriate, aldehydes are also formed.
- a powdery catalyst was used in this example.
- the catalyst can also be pressed into tablets, for example.
- Table 1 above shows that in the catalytic conversion of synthesis gas according to the invention, a comparatively high proportion of alcohols is obtained in addition to the alkenes.
- the proportion of alkanes in the product mixture is lower in comparison.
- the alkenes can also be converted to alcohols in the subsequent hydration step, so that, including the subsequent hydration step, the synthesis gas can be converted to alcohols with a CO selectivity of almost 60%, with primary alcohols (methanol, ethanol, 1-propanol and 1 -Butanol) from the alcohol synthesis and ethanol and secondary alcohols (2-propanol, 2-butanol and optionally 2-pentanol) can be obtained from the hydration step and the methanol content is comparatively low.
- Such an alcohol mixture is suitable, for example, as a fuel additive for admixture with gasoline. Alternatively, separation into the individual alcohols is possible.
- a possible method for separating the product mixture obtained in the catalytic conversion of synthesis gas is described below by way of example.
- the exemplary method for separation described below describes the separation of the mixture of alcohols, alkenes and alkanes obtained by the reaction of the synthesis gas from the gas phase and its subsequent separation into a mixture of alcohols and a mixture of hydrocarbons.
- the individual steps of this process for separating the product mixture can be varied and adapted to the product mixture obtained after the conversion. Inert gas removal
- a product stream is present at a temperature of 280 ° C. and a pressure of 60 bar. This is first expanded in a turbine to a pressure of 5 to 20 bar, preferably to about 10 bar, whereby electrical energy is obtained that can be used for the power requirement of the process.
- the subsequent gas-liquid separation which is used in particular to separate the inert gases (nitrogen) and unconverted components of the synthesis gas (hydrogen, carbon monoxide, carbon dioxide and methane), takes place by absorbing the product flow in a diesel oil (reference component Dodecane) or alternatively in an alkane or a hydrocarbon mixture with a comparatively low viscosity of, for example, less than 10 mPas at room temperature and preferably a comparatively high boiling point of in particular more than 200 ° C.
- the water is not absorbed, but largely condenses as a second liquid phase.
- the two liquid phases can then be separated in a decanter, whereby the hydrocarbons hardly go into the aqueous phase, but some of the alcohols.
- the alcohols can be distilled out of the water again as azeotropes by means of a first column. Alcohols and hydrocarbons are then desorbed from the diesel oil, which can be done in a column. After desorption, the diesel oil can be returned to the absorption process.
- a condensation of the low-boiling components can alternatively also come into consideration.
- the subsequent separation of alcohols and hydrocarbons is carried out by distillation in a second column, preferably at a high pressure of, for example, 10 bar to 40 bar, so that the C3 components still remain condensable in the presence of any residues of inert gas.
- This separation is preferably carried out in such a way that the hydrocarbons are practically completely removed from the alcohol fraction at the bottom, while lower alcohol contents (in particular methanol) in the hydrocarbons can be tolerated. If necessary, this process can be supported by a solubility-driven membrane.
- the hydrocarbons are obtained at the top at an increased pressure of, for example, 5 bar to 20 bar, while the remaining water and the alcohols dissolved therein are obtained and separated off in the bottom.
- This stream can be returned to the first distillation column to recover the alcohols.
- the condenser of the column can, for example, be a partial condenser.
- the outputs of the column are a gas phase made of hydrocarbons and inerts, a liquid phase made of hydrocarbons and an aqueous phase that can return to the column as reflux.
- the alcohol fraction can have a water content of, for example, about 10%. This water can be removed, for example, by means of a molecular sieve.
- An alternative method for removing the water from the alcohol fraction is extractive distillation, for example with ethylene glycol, which, however, requires a further separation step, since the water is drawn into the sump from the ethylene glycol, while the alcohols methanol and ethanol are practically anhydrous overhead. About half of the propanol remains and the butanol remains entirely in the bottom and these C3-C4 alcohols must also be removed from the ethylene glycol via the top in a subsequent column.
- the third alternative is pervaporation. Water passes selectively through a membrane and is withdrawn in vapor form as permeate. The energy consumption is even lower than with a molecular sieve.
- Another alternative method would be an azeotropic distillation, e.g. with butane or pentane as a selective additive.
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2019
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2020
- 2020-05-08 EP EP20726729.5A patent/EP4025549A1/de active Pending
- 2020-05-08 CN CN202080063228.9A patent/CN114364651A/zh active Pending
- 2020-05-08 US US17/640,069 patent/US20220306948A1/en active Pending
- 2020-05-08 WO PCT/EP2020/062858 patent/WO2021043452A1/de active Search and Examination
- 2020-08-14 US US17/640,092 patent/US12012371B2/en active Active
- 2020-08-14 CN CN202080062560.3A patent/CN114341082A/zh active Pending
- 2020-08-14 WO PCT/EP2020/072827 patent/WO2021043560A1/de unknown
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Also Published As
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CN114341082A (zh) | 2022-04-12 |
US20220306948A1 (en) | 2022-09-29 |
WO2021043452A1 (de) | 2021-03-11 |
DE102019213493A1 (de) | 2021-03-11 |
CN114364651A (zh) | 2022-04-15 |
WO2021043560A1 (de) | 2021-03-11 |
EP4025549A1 (de) | 2022-07-13 |
US12012371B2 (en) | 2024-06-18 |
US20220298088A1 (en) | 2022-09-22 |
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