WO2017207108A1 - Procédé et dispositif de fabrication d'éthanol - Google Patents

Procédé et dispositif de fabrication d'éthanol Download PDF

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Publication number
WO2017207108A1
WO2017207108A1 PCT/EP2017/025106 EP2017025106W WO2017207108A1 WO 2017207108 A1 WO2017207108 A1 WO 2017207108A1 EP 2017025106 W EP2017025106 W EP 2017025106W WO 2017207108 A1 WO2017207108 A1 WO 2017207108A1
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WO
WIPO (PCT)
Prior art keywords
ethanol
methanol
synthesis
synthesis gas
hydrogen
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Application number
PCT/EP2017/025106
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German (de)
English (en)
Inventor
Andreas Peschel
Andreas Obermeier
Original Assignee
Linde Aktiengesellschaft
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 Aktiengesellschaft filed Critical Linde Aktiengesellschaft
Publication of WO2017207108A1 publication Critical patent/WO2017207108A1/fr

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    • 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
    • C07C29/15—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
    • 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
    • C07C29/1516—Multisteps
    • 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
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups

Definitions

  • the invention relates to a process and a plant for the production of ethanol from synthesis gas according to the preambles of the independent claims.
  • ethanol is currently predominantly fermentative from biomass.
  • synthesis gas can also be converted to ethanol by fermentation.
  • Corresponding processes are also referred to as gas fermentation and are described, for example, in Brown, R.C .: “Biorenewable Resources: Engineering New Products from Agriculture”, Arnes, Iowa State Press, 2008.
  • the chemical synthesis of ethanol from synthesis gas is also known. It can be carried out, for example, via the intermediate methanol, which is then homologated to ethanol and possibly other higher alcohols. Corresponding methods are disclosed in US 4,882,360 A and US 2013/0123377 A1. Another route is the conversion of methanol to acetic acid and the subsequent hydrogenation of acetic acid to ethanol. Examples include the so-called TCX and the so-called SaaBre process. The production of ethanol by carbonylation of methanol or the hydration of ethylene is also known.
  • Synthesis gas and the selectivity to ethanol are relatively low. Also, the catalyst systems used are very expensive by the use of precious metals, especially rhodium.
  • the present invention therefore has the object to improve known processes for the production of ethanol from synthesis gas.
  • the present invention is based on the finding that it is particularly advantageous not to supply synthesis gas directly to an ethanol direct synthesis reactor for the direct synthesis of ethanol, but to partially react the synthesis gas initially in a prereactor in the form of a methanol synthesis reactor and to produce methanol there. In this way, in the context of the present invention as a whole an increased synthesis gas conversion can be achieved. This is unexpected, since initially it would have been suspected that by using an additional
  • the present invention proposes a process for the production of ethanol from synthesis gas using an ethanol direct synthesis reactor equipped with a catalyst designed to directly convert carbon monoxide with hydrogen and / or carbon dioxide with hydrogen to ethanol as the main product.
  • a "synthesis gas” is understood to mean a gas mixture which contains at least predominantly carbon monoxide and hydrogen. More details are given below.
  • ethanol is synthesized at least in part without the formation of removable intermediates from carbon monoxide and hydrogen. Possibly formed in the direct synthesis of ethanol intermediates react at least partially, especially still on
  • a process for the direct synthesis of ethanol therefore differs from the above-mentioned process for the two-stage synthesis of methanol or acetic acid, which are formed as separately handled and especially separable intermediates and then further reacted.
  • the synthesis gas is first a methanol synthesis reactor, which is equipped with a catalyst which is designed to convert carbon monoxide with hydrogen and / or carbon dioxide with hydrogen to methanol as the main product is supplied, and that a methanol synthesis reactor extracted component mixture at least partly unseparated
  • Ethiloldirektsynthesereaktor is supplied.
  • the methanol synthesis reactor is therefore in the context of the present invention directly upstream of the
  • Methanol synthesis reactor is fed without separation to the ethanol direct synthesis reactor. However, it can be between the methanol synthesis reactor and the
  • Ethanol direct synthesis reactor recycled methanol can be fed. Furthermore, optionally recirculated or freshly used carbon dioxide can be fed.
  • the component mixture supplied to the ethanol direct synthesis reactor comprises at least all components of the methanol synthesis reactor, apart from changes caused, for example, by further reactions
  • Methanol synthesis reactor extracted component mixture without material Separation between the mentioned synthesis reactor can be discharged.
  • no active pressure influencing between the synthesis reactors so no compression or relaxation.
  • a temperature influence for example by cooling or heating, may also be provided within the scope of the invention.
  • Carbon monoxide is formed with hydrogen and / or of carbon dioxide with hydrogen to ethanol as the main product ", is understood hereunder that under the influence of the catalyst, a direct reaction of carbon monoxide with hydrogen to ethanol takes place without the formation of separable intermediates, as already explained above.
  • a main product of a synthesis is here understood to mean a product which has a molar fraction of more than 10%, in particular more than 10%, more than 20%, more than 30%, more than 40%, more than 50%, more than 60% %, more than 70%, more than 80% or more than 90%, based on all formed in the synthesis
  • Products includes. If, for example, 50% ethanol and 50% methanol are formed in a direct synthesis of ethanol, the ethanol formed is still one or one of the main products of the synthesis.
  • methanol is also formed, but preferably only small amounts of other, ie higher, alcohols. These therefore preferably form only by-products. However, if necessary, not inconsiderable amounts of methane are formed.
  • the particular product spectrum formed depends essentially on the catalyst used.
  • a mixture "predominantly" contains one or more components is below understood that the mixture contains the one or more components to at least 40%, 50%, 60%, 70%, 80%, 90%, 95% or 99%.
  • Methanol synthesis reactors which are equipped with a catalyst which is designed to convert carbon monoxide with hydrogen and / or carbon dioxide with hydrogen to methanol as the main product
  • a catalyst which is designed to convert carbon monoxide with hydrogen and / or carbon dioxide with hydrogen to methanol as the main product
  • the skilled worker also known from the prior art, for example from the article "methanol” in Ullmann's Encyclopedia of Industrial Chemistry, Online Edition October 15, 2012, DOI: 10.1002 / 14356007.a16_465.pub3, Section 4.2, "Catalysts”.
  • Catalyst which is "designed to convert carbon monoxide with hydrogen and / or carbon dioxide with hydrogen to methanol as the main product", the above applies accordingly.
  • methanol is formed as the main product in the illustrated sense, but not or only slightly ethanol.
  • Ethanol is preferably formed only in a molar proportion of at most 1%, 0.5% or 0.01% based on the total products. This distinguishes a corresponding catalyst from the catalysts for the direct synthesis of ethanol, which provide ethanol as the main product and also methanol in significant amounts.
  • carbon dioxide also reacts with hydrogen, with either ethanol or methanol being the main product. Further details on the reactions taking place in corresponding reactors are explained below.
  • An ethanol direct synthesis reactor as can be used in the context of the present invention, can be operated, for example, at a pressure of 20 to 100 bar and a temperature of 200 to 300 ° C. Typical conditions and catalysts are given in the cited literature.
  • a catalyst is used in the methanol synthesis reactor, which is formed into a corresponding reaction.
  • the ethanol synthesis reactor therefore, the overall yield of ethanol can be increased.
  • the ethanol synthesis reactor can be made smaller and requires smaller amounts of expensive and limited available noble metal catalysts.
  • a methanol synthesis reactor as it can be used in the context of the present invention, for example, at a pressure of 20 to 100 bar and a temperature of 180 to 280 ° C are operated. A portion of the synthesis gas converts to methanol in the methanol synthesis reactor; In addition, the water gas shift reaction takes place:
  • the subject of the present invention is an improved reactor connection for the synthesis of ethanol from synthesis gas.
  • Vorschscnies a Methanolsyntheserea ktors before a Ethanoldirektsynthesereaktor the total synthesis gas sales can be increased because a part of the
  • Synthesis gas is converted in the methanol synthesis reactor to methanol.
  • the space-time yield in the ethanol direct synthesis can be increased in comparison to known processes.
  • the Ethanol direct synthesis reactor can therefore be formed significantly smaller than in conventional methods for ethanol direct synthesis.
  • Ethanoldirektsynthesereaktors to be processed residual amounts of synthesis gas are smaller, a corresponding separation is therefore easier.
  • Ethanol direct synthesis reactor Therefore, here is a smaller amount of gas separation technology to work. Since the methanol synthesis, but also the ethanol direct synthesis, which is used in the present invention, are clearly exothermic, a particularly advantageous temperature control can be achieved by using a smaller Ethanoldirektsynthesereaktors with upstream methanol synthesis reactor instead of only a larger synthesis reactor, since each heat individually and Also downstream of the respective synthesis reactor can be discharged. This is reflected in an even higher efficiency of the synthesis reactors again and also in reduced costs, since, for example, the pipes as
  • Synthesis reactors used tube bundle reactors can each be optimally designed and tempered.
  • methanol is formed as a by-product and is therefore present in a component mixture which can be taken from the ethanol direct synthesis reactor. Further methanol in this component mixture is methanol from the methanol synthesis reactor, which was not reacted in the ethanol direct synthesis reactor. Corresponding methanol can therefore from the
  • Ethanoldirektsynthesereaktor removed component mixture can be separated. To increase the ethanol yield, this methanol can the
  • Ethanoldirektsynthesereaktor be fed back.
  • a portion of the methanol formed in the ethanol direct synthesis reactor and the methanol present in the inlet stream of the ethanol direct synthesis reactor are converted to ethanol and optionally higher alcohols.
  • the methanol can also be recovered as a product.
  • the present invention provides in this variant a process for the combined production of ethanol and methanol.
  • the gas volume to be processed in the separation is significantly reduced in each case, the separation thus easier and less expensive.
  • Ethanoldirektsynthesereaktor one or more by-products of the methanol and / or the ethanol direct synthesis and / or one or more unreacted components of the synthesis gas separated. This is advantageous for the reason mentioned several times, because reduced volumes have to be processed at this point due to the improved overall conversion.
  • the or at least one of the further by-products and / or the or at least one of the further unreacted components of the synthesis gas can, depending on the usability, at least partly in the process, ie in the
  • the use can be material, i. in a process stream whose components are converted to methanol or ethanol, but also energetically, for example by burning methane done.
  • Ethanol direct synthesis reactor existing gas stream to recycle without that inert components accumulate excessively in a corresponding circuit.
  • Multicomponent mixture with, for example, hydrogen, carbon dioxide and / or methane.
  • material problems can be avoided by excessive carbon monoxide.
  • This is, for example, what is known as metal dusting, that is to say a form of high-temperature corrosion, which may occur at, for example, about 300 to 850.degree.
  • Corresponding measures are therefore advantageously taken when a preheating of a corresponding gas mixture is made to the temperatures mentioned.
  • the carbon monoxide is partially converted in the component mixture using a Wasserergasshift to carbon dioxide.
  • the process used in the context of the present invention may in particular also comprise the provision of the synthesis gas by means of suitable reactions.
  • steam reforming dry reforming, autothermal reforming and partial oxidation
  • An appropriate provision of the synthesis gas advantageously also comprises the treatment and / or conditioning of the synthesis gas and / or an insert used to provide the synthesis gas, for example by desulfurization, compression, heat integration, the condensation of process water and / or carbon dioxide separation. Also, such steps help to provide a synthesis gas having optimum composition for the present invention.
  • An appropriate provision of the synthesis gas advantageously also comprises the treatment and / or conditioning of the synthesis gas and / or an insert used to provide the synthesis gas, for example by desulfurization, compression, heat integration, the condensation of process water and / or carbon dioxide separation. Also, such steps help to provide a synthesis gas having optimum composition for the present invention.
  • the stoichiometric number SN is calculated from the mole fractions x of hydrogen, carbon dioxide and
  • Carbon monoxide to SN (x H2 - x CO2) / (x CO + x CO2).
  • the synthesis gas may in addition to hydrogen and carbon monoxide in particular also 0 to 20 mole percent carbon dioxide.
  • the methane content can be up to 10 or up to 20 mole percent. Further components are advantageously at most 10 mole percent, contain at most 5 mole percent or at most 1 mole percent.
  • the stated stoichiometric number range and the stated contents are influenced by feeds, returns and the like. The values given apply to the synthesis gas supplied to the methanol synthesis reactor and the corresponding ones
  • the ethanol direct synthesis in the context of the present invention is carried out catalytically, in particular as explained above.
  • the ethanol direct synthesis reactor (s) are therefore designed for catalytic ethane direct synthesis using a rhodium, manganese, ruthenium, iron, palladium, platinum or any combination of said catalyst and optionally one or more other materials.
  • the present invention also extends to a plant for the production of ethanol from synthesis gas, with an ethanol direct synthesis reactor equipped with a catalyst suitable for direct conversion of carbon monoxide
  • a methanol synthesis reactor which is equipped with a catalyst which is designed to react carbon monoxide with hydrogen and / or from carbon dioxide with hydrogen to methanol as the main product.
  • means are provided which are adapted to
  • Methanol synthesis reactor taken component mixture at least partially unseparated the Ethanoldirektsynthesereaktor.
  • a corresponding system for implementing a method is set up, as has been explained above, and has corresponding means.
  • the features and advantages explained above are therefore expressly referred to.
  • FIG. 1 illustrates a method according to an embodiment of the invention.
  • FIG. 1 shows a method according to an embodiment of the invention
  • FIG. 1 thus relate to a corresponding installation in the same way.
  • a hydrocarbon-rich feed stream a is fed to one or more synthesis reactors 1 for the production of synthesis gas or other technical equipment and corresponding process steps.
  • a steam reforming, a dry reforming, an autothermal reforming and a partial oxidation can be used to provide synthesis gas.
  • combinations of these reactions are possible, such as the
  • a corresponding provision of the synthesis gas advantageously also comprises the conditioning and / or conditioning of the
  • Synthesis gas and / or one used to provide the synthesis gas use, for example, by desulfurization, compression, heat integration, the condensation of process water and / or carbon dioxide separation. All explained method steps can also be used in the context of the method 100.
  • other material streams for example steam or oxygen, can also be used as required.
  • a synthesis gas stream b is provided, which is fed to a methanol synthesis reactor 2.
  • a methanol synthesis reactor 2 For technical details regarding the methanol synthesis reactor 2, in particular the reaction conditions and the catalysts used, reference is made to the cited technical literature and the above explanations.
  • the methanol synthesis reactor 2 a stream is removed c containing unreacted components of the synthesis gas of the stream b and methanol and by-products of the methanol synthesis. This is fed, in particular together with a recycle stream d explained below, to an ethanol direct synthesis reactor 3.
  • the ethanol direct synthesis reactor 3 may be adapted for catalytic ethanol direct synthesis using a rhodium, manganese, ruthenium, iron, palladium, platinum or a combination of any of said metals and optionally one or more other catalyst materials.
  • the Ethanoldirektsynthesereaktor 3 leaves a stream e, in addition to ethanol by-products of the ethanol direct synthesis and unreacted components of the synthesis gas or unreacted and reacted components from the stream contains c or d.
  • Ethanoldirektsynthesereaktors 3 where the stream e is supplied, is separated from this, for example, a methanol-rich stream f, which at least partially executed as a product stream from the process and / or at least partially used as the recycle stream d.
  • a methanol-rich stream f which at least partially executed as a product stream from the process and / or at least partially used as the recycle stream d.
  • Stream d and f the same composition. Furthermore, an ethanol-rich stream g and a water-rich stream h can be separated.
  • the one or more separators 4 may operate using known separation principles, for example, distillation, condensing, absorptive, and the like.
  • a residual current i Downstream of the one or more separators 5 remains a residual current i, which may still contain, for example, hydrogen, methane, carbon monoxide and carbon dioxide.
  • the carbon monoxide contained in the residual stream i can
  • All components can, as already explained, separated and used in a suitable manner, for example as recycling streams.

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

Abstract

L'invention concerne un procédé (100) de fabrication d'éthanol à partir d'un gaz de synthèse à l'aide d'un réacteur de synthèse directe d'éthanol (3), qui est équipé d'un catalyseur, lequel assure la conversion directe de monoxyde de carbone et d'hydrogène et/ou de dioxyde de carbone et d'hydrogène en éthanol en tant que produit principal. L'invention prévoit que le gaz de synthèse soit tout d'abord cédé à un réacteur de synthèse de méthanol (2) équipé d'un catalyseur qui assure la conversion de monoxyde de carbone et d'hydrogène en méthanol en tant que produit principal, et qu'un mélange de constituants prélevé du réacteur de synthèse de méthanol (2) soit cédé au moins en partie de manière non séparée au réacteur de synthèse directe d'éthanol (3). L'invention concerne également une installation correspondante.
PCT/EP2017/025106 2016-06-01 2017-05-04 Procédé et dispositif de fabrication d'éthanol WO2017207108A1 (fr)

Applications Claiming Priority (2)

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DE102016006710.1 2016-06-01
DE102016006710.1A DE102016006710A1 (de) 2016-06-01 2016-06-01 Verfahren und Anlage zur Herstellung von Ethanol

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009009389A2 (fr) * 2007-07-09 2009-01-15 Range Fuels, Inc. Procédés et appareil pour produire des alcools à partir d'un gaz de synthèse
WO2012003901A1 (fr) * 2010-07-05 2012-01-12 Haldor Topsøe A/S Procédé pour la préparation d'éthanol et d'alcools supérieurs

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4882360A (en) 1984-07-30 1989-11-21 The Dow Chemical Company Process for producing alcohols from synthesis gas

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009009389A2 (fr) * 2007-07-09 2009-01-15 Range Fuels, Inc. Procédés et appareil pour produire des alcools à partir d'un gaz de synthèse
WO2012003901A1 (fr) * 2010-07-05 2012-01-12 Haldor Topsøe A/S Procédé pour la préparation d'éthanol et d'alcools supérieurs

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