EP3679006A1 - Procédé pour réguler l'hydrogénation catalytique de 1,4-butynediol par l'intermédiaire de la teneur en co et/ou ch4 du flux de gaz résiduaires - Google Patents

Procédé pour réguler l'hydrogénation catalytique de 1,4-butynediol par l'intermédiaire de la teneur en co et/ou ch4 du flux de gaz résiduaires

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Publication number
EP3679006A1
EP3679006A1 EP18758629.2A EP18758629A EP3679006A1 EP 3679006 A1 EP3679006 A1 EP 3679006A1 EP 18758629 A EP18758629 A EP 18758629A EP 3679006 A1 EP3679006 A1 EP 3679006A1
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EP
European Patent Office
Prior art keywords
catalyst
exhaust gas
reaction zone
content
hydrogenation
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.)
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Application number
EP18758629.2A
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German (de)
English (en)
Inventor
Rolf Pinkos
Jens Weiguny
Jens Baldamus
Michael Schwarz
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3679006A1 publication Critical patent/EP3679006A1/fr
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Classifications

    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C07C31/207—1,4-Butanediol; 1,3-Butanediol; 1,2-Butanediol; 2,3-Butanediol

Definitions

  • the present invention relates to a process for the preparation of 1, 4-butanediol by catalytic hydrogenation of 1, 4-butynediol in a reaction zone with hydrogen in the presence of a heterogeneous hydrogenation catalyst, wherein the content of the exhaust gas stream of at least one gas selected from CO and CH 4 , and uses the content of the exhaust gas flow to the measured gas to control the hydrogenation.
  • catalytic hydrogenation is one of the most important reactions for the production of chemical products.
  • the hydrogenation is preferably carried out in the presence of heterogeneous catalysts, which are easier to separate from the reaction mixture in contrast to homogeneous catalysts.
  • a very important industrial process is the hydrogenation of butynediol to butanediol.
  • Butanediol is used for the preparation of tetrahydrofuran (THF), polyTHF, polyesters, etc.
  • the hydrogenation of butynediol to butanediol is usually carried out in two stages in large-scale processes. The second stage is almost always a fixed bed reactor operated at high pressure.
  • the US 6,262,317 (DE 196 41 707 A1) describes the hydrogenation of 1, 4-butynediol with hydrogen in the liquid continuous phase in the presence of a heterogeneous hydrogenation catalyst at temperatures of 20 to 300 ° C, a pressure of 1 to 200 bar and values of liquid-side volume-related mass transfer coefficient kl_a of 0.1 s _1 to 1 s _1 .
  • the reaction can be carried out either in the presence of a catalyst suspended in the reaction medium or in a fixed-bed reactor operated in cocurrent in a cyclic gas mode.
  • Example 1 a continuous hydrogenation of 100 g / h of a 54% strength by weight butynediol solution at 35 bar hydrogen and 149 ° C.
  • 3,449,445 describes a process for the hydrogenation of butynediol on a Raney nickel suspension catalyst at 50 to 60 ° C. and 14 to 21 bar in a semi-batch mode.
  • Each Raney Nickel Catalyst Charge can be used for approximately 20 to 40 batch hydrogenations before replacement.
  • the catalyst is allowed to settle.
  • the product is decanted off and filtered and then post-hydrogenated on a fixed catalyst bed at 120 to 140 ° C and 138 to 207 bar (2000 to 3000 psig).
  • the content of the product of butenediol, ie a partially hydrogenated intermediate a measure of the activity of the hydrogenation catalyst and their decrease with increasing life.
  • DE-A 2 004 61 1 describes the continuous hydrogenation of butynediol on a Raney nickel fixed-bed catalyst at preferably 210 to 360 bar hydrogen partial pressure and a temperature of 70 to 145 ° C.
  • the temperature at the reactor outlet should not exceed 150 ° C, in order to avoid excessive formation of by-products (mainly n-butanol).
  • the heat of reaction is described to lead the reaction mixture in a circulation stream and to remove this heat.
  • the ratio of fed in the circulation stream reaction mixture to freshly fed feed in the range of 10: 1 to 40: 1, preferably 15: 1 to 25: 1
  • other methods for heat removal such as a stepwise reaction with heat removal between the individual stages , described.
  • the average by-products can be reduced from 6.6% in the first hydrogenation to 4.1% in the second hydrogenation.
  • the butenediol content in the crude product is suitable as a measure of the activity or deactivation of the catalyst.
  • a disadvantage of this method is that the butenediol content in the crude product must be measured consuming offline and the butenediol must then be hydrogenated as completely as possible in a post-hydrogenation to butanediol. It is basically known to carry out hydrogenation reactions in the presence of carbon monoxide (CO).
  • the CO can be added to the hydrogen used for the hydrogenation and / or originate from the starting materials or their intermediates, by-products or products. If catalysts are used for hydrogenation which contain CO-sensitive active components, it is known as a countermeasure to carry out the hydrogenation at a high hydrogen pressure and / or a low catalyst load. Otherwise, the implementation may be incomplete, so that z. For example, a secondary reaction in at least one further reactor is absolutely necessary.
  • a palladium catalyst is used (preferably on a support) for the selective hydrogenation of 1, 4-butynediol to 1, 4-butenediol.
  • the palladium catalyst is pretreated before the actual reaction with carbon monoxide (about 200 to 2000 ppm CO) and about one equivalent of hydrogen and then for the selective hydrogenation of butynediol to butenediol at a pressure of 1 to 20 bar and a Temperature used from room temperature to 100 ° C. It is assumed that CO binds more strongly on the catalyst surface than butenediol, but weaker than butynediol.
  • the hydrogenation of butynediol to butenediol is favored, the hydrogenation of butenediol to butanediol, however, inhibited. Only when butynediol is completely hydrogenated, the formed butenediol is further hydrogenated to butanediol. In this particular case, the inhibitory effect of CO on the catalyst is desired. In the case of hydrogenation of butynediol to butanediol, however, it is highly undesirable.
  • No. 4,361,495 describes a process for the regeneration of deactivated supported nickel catalysts used in the posthydrogenation of crude butanediol from butynediol hydrogenation.
  • the nickel catalyst used optionally contains copper and / or manganese and / or molybdenum on a support material such as alumina or silica and is generally deactivated after hydrogenation of from 500 to 2000 kg of butanediol per kg of catalyst so that it must be replaced.
  • the deactivated catalyst is treated at 200 to 500 ° C for about 15 h at atmospheric pressure in a hydrogen stream.
  • DD 265 396 A1 a process for the preparation of butanediol by hydrogenation of butynediol is described, wherein the reaction by controlling the Butanolkonzentrati- on in the hydrogenation product by means of the catalyst metering is controlled.
  • 35% butynediol is hydrogenated at 10 bar hydrogen pressure and 50 ° C on a Pd catalyst (catalyst concentration of 60 g / L) to butanediol, wherein the butynediol dosing rate was 1 kg of butynediol per kg of Pd catalyst , Throughout the experiment, Pd catalyst was continuously withdrawn from the reaction vessel and fresh catalyst added.
  • the measured butanol concentration in the hydrogenation effluent served as a measure of the metering rate: If the butanol content in the hydrogenation product fell, a larger amount of catalyst was added, while less catalyst was added with increasing butanol contents. The target range for the amount of butanol was 0.03 to 0.3%. Less than 0.1% butenediol was found in the hydrogenation product. Thus, the butanol concentration served as a control parameter in Butindiolhydrierung to intervene in the hydrogenation such that the product quality could be kept constant. Again, a laborious offline measurement of the butanol concentration of the hydrogenation effluent was necessary.
  • the present invention has for its object to provide an improved process for the preparation of 1, 4-butanediol by catalytic hydrogenation of 1, 4-butynediol available that overcomes as many of the aforementioned disadvantages.
  • the invention relates to a process for the preparation of 1, 4-butanediol by catalytic hydrogenation of 1, 4-butynediol in a reaction zone with hydrogen in the presence of a heterogeneous hydrogenation catalyst at a temperature in the range of 20 to 300 ° C and a pressure in the range of From 1 to 200 bar, in which the hydrogen is added to the reaction zone and an exhaust gas flow is discharged from the reaction zone and the content of the exhaust gas stream is measured on at least one gas, selected from CO, and CH 4 , whereby a target value for the content of the exhaust gas flow at the determines measured gas,
  • 1,4-butanediol is prepared by catalytic hydrogenation of 1,4-butynediol in a reaction zone with hydrogen in the presence of a heterogeneous hydrogenation catalyst, in which the content of the exhaust gas stream is selected from at least one gas chosen from CO and CH 4 , measures and uses the content of the exhaust gas flow to the measured gas to control the hydrogenation.
  • control means a process in which a continuous
  • the controlled variable (actual value), detected, compared with another variable, the reference variable (setpoint), and is influenced in the sense of an approximation to the reference variable.
  • the control deviation as the difference between the actual value and the setpoint value is fed to the controller, which forms a manipulated variable.
  • the manipulated variable is the output (the position) of the actuator used, with the aid of a targeted intervention in the control path takes place.
  • the actuator may be part of the regulator, but in many cases it is a separate device.
  • Controlled variable in the process according to the invention is the content of the exhaust gas in a particular gas (CO, CH 4 ).
  • Examples of actuators are valves, switches, etc.
  • An example of the manipulated variable is the opening state of a valve. Its manipulated variable is, for example, the position of the handwheel with which the valve is operated.
  • the exhaust gas values can be measured either offline or online, particularly preferred is the online measurement.
  • CO sensors Conventional carbon monoxide sensors known to those skilled in the art can be used to measure the CO content. These can be based on optochemical detection, infrared measurement, thermal conductivity measurement, heat tone measurement, electrochemical processes or on semiconductor-based sensors. Preference is given to using electrochemical sensors, sensors based on semiconductors or non-dispersive infrared sensors.
  • a decreasing or no longer sufficient catalyst activity manifests itself in addition to an increased CO content or a lower CH 4 content in the exhaust gas stream also in the incomplete hydrogenation of butynediol and / or increasing levels in the product of 1, 4-butenediol, 4-hydroxybutyraldehyde, 2 - (4-hydroxybutoxy) tetrahydrofuran (hereinafter called acetal) and ⁇ -butyrolactone (hereinafter called GBL).
  • decreasing or no longer sufficient catalyst activity manifests itself in decreasing pH values and increasing APHA numbers in the product stream, the can also be measured online and can also be used as a measure of the catalyst activity.
  • Suitable hydrogenation catalysts for the process according to the invention for the preparation of 1,4-butanediol by catalytic hydrogenation of 1,4-butynediol are those catalysts which are suitable for hydrogenating C-C triple bonds and C-C double bonds to single bonds. They usually contain one or more elements of groups 6 to 1 1 of the Periodic Table of the Elements. Preferably contain the
  • Catalysts at least one element (first metal) selected from Ni, Cu, Fe, Co, Pd, Cr, Mo, Mn, Re, Ru, Pt and Pd. More preferably, the catalysts contain at least one element (first metal) selected from Ni, Cu, Fe, Co, Pd and Cr. In a specific embodiment, the catalysts contain Ni.
  • the hydrogenation catalyst additionally contains at least one promoter element.
  • the promoter element is selected from Ti, Ta, Zr, V, Nb, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn. Cd, Ce and Bi. It is possible that the hydrogenation catalyst contains at least one promoter element which simultaneously fulfills the definition of a first metal in the sense of the invention.
  • promoter elements are selected from Ni, Fe, Co, Cu, Cr, Pt, Ag, Au, Pd, Mn, Re, Ru, Rh and Ir.
  • the hydrogenation catalyst contains, based on the reduced metallic form, a major amount (ie, more than 50% by weight) of the first metal and a minor amount (ie, less than 50% by weight) of a different metal as a promoter element.
  • a major amount ie, more than 50% by weight
  • a minor amount ie, less than 50% by weight
  • the hydrogenation catalyst contains exclusively a promoter element or more than one promoter element selected from Ti, Ta, Zr, V, Mo, W, Bi and Ce.
  • the hydrogenation catalyst contains Mo as a promoter element.
  • the hydrogenation catalyst contains Mo as the sole promoter element.
  • the hydrogenation catalyst based on the reduced metallic form, contains a first metal in an amount of 0.1 to 100% by weight, preferably 0.2 to 99.5% by weight, particularly preferably 0.5 to 99% by weight .-%.
  • the promoter content of the catalyst is generally up to 25 wt .-%, preferably 0.001 to 15 wt .-%, particularly preferably 0.01 to 13 wt .-%.
  • Raney catalysts are alloys containing at least one catalytically active metal and at least one alkali-soluble (leachable) alloy component.
  • Typical catalytically active metals include, for example, Ni, Fe, Co, Cu, Cr, Pt, Ag, Au and Pd, and typical leachable alloy components are e.g. B. Al, Zn and Si.
  • Such Raney metal catalysts and processes for their preparation are, for. In US 1, 628,190,
  • Raney metal alloys Prior to their use in heterogeneously catalyzed chemical reactions, especially in a hydrogenation reaction, Raney metal alloys generally require activation.
  • Conventional methods for activating Raney metal catalysts include grinding the alloy into a fine powder if it is not already powdered by the prior art. For activation, the powder is subjected to treatment with an aqueous liquor, wherein the leachable metal is partially removed from the alloy and the highly active non-leachable metal remains.
  • carrier materials for supported catalysts aluminum oxides, titanium dioxides, zirconium dioxide, silicon dioxide, clays, for.
  • silicates such as magnesium or aluminum silicates, zeolites and activated carbons are used.
  • Preferred support materials are aluminas, titanium dioxides, silica, zirconia and activated carbons.
  • mixtures of various carrier materials can also serve as carriers for catalysts which can be used in the process according to the invention.
  • These catalysts can be used either as shaped catalyst bodies, for example as spheres, cylinders, rings, spirals, or in the form of powders.
  • the catalysts are preferably used as shaped bodies. Suitable catalysts for the hydrogenation are described, for example, in DE-A 12 85 992, DE-A 25 36 273, EP-A 177 912, EP-A 394 841, EP-A 394 842, US Pat. No. 5,068,468, DE-A 1 641 707 and US Pat
  • EP-A-0 068 862, EP-A-0 198 435, EP-A 201 614 and EP-A 448 884 are described.
  • EP 2 764 916 A1 describes hydrogenation catalysts based on foam-shaped shaped catalyst bodies.
  • the hydrogenation catalysts can be used in a fixed bed or in suspension. If the catalysts are arranged in the form of a fixed bed, the reactor can be operated in trickle mode or in the upflow mode. In a specific embodiment, the catalyst is arranged in the form of a packed bed and is operated in an upward direct current of liquid and gas. Specifically, then the liquid and not the gas is present as a continuous phase.
  • the inventive method is preferably carried out with technical 1, 4-butynediol.
  • This is in the form of an aqueous solution and may contain insoluble or dissolved components from the 1,4-butynediol synthesis. These include z. As copper, bismuth, aluminum or silicon compounds.
  • purified 1, 4-butynediol can also be used in the process according to the invention.
  • the purification of crude 1, 4-butynediol is z. B. by distillation.
  • 1, 4-butynediol can be prepared industrially from acetylene and aqueous formaldehyde and is usually hydrogenated as an aqueous 30 to 60 wt .-% solution.
  • alcohols such as methanol, ethanol, propanol, butanol or 1, 4-butanediol are hydrogenated.
  • the hydrogen required for the hydrogenation is preferably used purely, but it can also admixtures of other gases, such as. As methane and carbon monoxide.
  • a pressure-resistant reactor for the hydrogenation by the process according to the invention are in principle pressure-resistant reactors, as they are usually used for exothermic, heterogeneous reactions with the introduction of a gaseous and a liquid starting material.
  • These include the commonly used reactors for gas-liquid reactions, such as. B. tube reactors, tube bundle reactors and gas circulation reactors.
  • a special embodiment of the tube reactors are shaft reactors.
  • Such reactors are known in principle to the person skilled in the art.
  • a cylindrical reactor with verti- Longitudinal axis is used, which has at the bottom or top of the reactor one or more inlet devices for feeding a reactant mixture containing at least one gaseous and at least one liquid component.
  • Partial streams of the gaseous and / or the liquid educt may, if desired, additionally be fed to the reactor via at least one further feed device.
  • the hydrogenation reaction mixture is generally present in the reactor in the form of a two-phase mixture having a liquid and a gaseous phase.
  • the processes according to the invention are particularly suitable for hydrogenations which are to be carried out on an industrial scale.
  • the reactor then preferably has an internal volume in the range from 0.1 to 100 m 3 , preferably from 0.5 to 80 m 3 .
  • the term internal volume refers to the volume including the fixed catalyst beds present in the reactor and optionally further existing internals.
  • the technical advantages associated with the process according to the invention are also already apparent in reactors with a smaller internal volume.
  • the reaction zone is generally traversed by a two-phase gas / liquid mixture.
  • the feed of the educts in the reaction zone is usually in
  • the exhaust gas can be removed to remove the accumulation of Inert really kind a partial flow and discharged.
  • the exhaust gas is at least partially guided in a circulation stream (cycle gas mode).
  • the cycle gas method the exhaust gas leaving the reaction zone, optionally after discharge of a partial flow to avoid accumulation of Inert dealt precisely and optionally after addition of fresh hydrogen, recycled into the reactor.
  • the return takes place z. B. via a compressor. It is possible to lead the entire cycle gas quantity or a subset thereof via a propulsion jet compressor.
  • the cycle gas compressor is replaced by a low-cost nozzle.
  • the liquid discharge is at least partially subjected to the isolation of a product stream containing the crude 1, 4-butanediol.
  • the liquid discharge is guided at least partially in a circulation stream. In this case, the liquid discharge is recycled after removal of a partial flow as a product stream and optionally after passing through a heat exchanger to remove heat of reaction in the reactor.
  • the content of the exhaust gas stream is measured on at least one gas chosen from CO and CHU. If separation of the two-phase gas / liquid mixture emerging from the reaction zone already takes place in the reactor, the gas content in the gas phase in the reactor can be measured before it is discharged as an exhaust gas stream. It is also possible that the measurement of the gas content in the exhaust gas flow from the reactor. With cycle gas mode, it is also possible that the measurement of the gas content in the recycle gas takes place before the supply of fresh hydrogen. If gas and liquid are discharged together from the reactor and only then a gas / liquid T rennung is made, the measurement of the gas content in the after phase separation of the
  • the temperature in the hydrogenation is preferably in a range of 20 to 300 ° C, particularly preferably 40 to 250 ° C.
  • the absolute pressure in the hydrogenation is preferably in a range from 1 to 350 bar, more preferably in a range from 5 to 300 bar.
  • the temperature in the hydrogenation is preferably in a range from 30 to 300.degree. C., particularly preferably from 50 to 250.degree. C., in particular from 70 to 220.degree.
  • the pressure in the hydrogenation is preferably in a range from 25 to 350 bar, more preferably from 100 to 300 bar, in particular from 150 to 300 bar.
  • the temperature in the hydrogenation is preferably in a range from 20 to 300.degree. C., more preferably from 60 to 200.degree. C., in particular from 120.degree. C. to 180.degree.
  • the pressure in the hydrogenation is preferably in a range from 1 to 200 bar, more preferably from 5 to 150 bar, in particular from 20 to 100 bar.
  • the molar ratio of hydrogen fed to the reaction zone from the reaction zone to the reaction zone fed to 1, 4-butynediol is preferably at least 2: 1.
  • the molar ratio of hydrogen fed to the reaction zone from the reaction zone to the reaction zone supplied 1,4-butynediol is preferably in a range of 2.01: 1 to 4: 1, more preferably 2.01: 1 to 3: 1 and most preferably 2, 01: 1 to 2.6: 1.
  • the molar ratio of hydrogen fed to the reaction zone to the reaction zone is 1,4-butynediol, which is 2.2: 1 to 2.4: 1.
  • the hydrogenation reaction mixture is at least partially conducted in a liquid recycle stream. Then, the molar ratio of the reaction zone freshly supplied hydrogen to the reaction zone freshly supplied 1, 4-butynediol is preferably at least 2: 1.
  • the molar ratio of freshly supplied hydrogen to the reaction zone of freshly fed 1,4-butynediol is preferably in the range from 2.01: 1 to 4: 1, particularly preferably 2.01: 1 to 3: 1 and most preferably 2.01: 1 to 2.6: 1.
  • the molar ratio of freshly fed hydrogen to the reaction zone from the reaction zone is 1, 4-butynediol, 2.2: 1 to 2.4: 1.
  • the ratio of gas stream supplied to the reactor to the reactor stream is preferably in the range from 0.99: 1 to 0.4: 1. In other words, at least 60% of the gas supplied leaves the reactor system. Thus, it can be avoided in Kreisgasfahrweise that aufpegeln unwanted components such as CO in the gas stream.
  • the conversion of 1,4-butynediol is preferably 90 to 100%, more preferably 98 to 100%, in particular 99.5 to 100%.
  • the yield of 1,4-butanediol obtained by catalytic hydrogenation of 1,4-butynediol is lower than the conversion of 1,4-butynediol since there are other by-products, such as, for example, propanol, butanol, hydroxybutyraldehyde, acetal,
  • ⁇ -butyrolactone GBL
  • the inventive method allows a high selectivity with respect to the target compound 1, 4-butanediol.
  • Increased butenediol contents are generally accompanied by elevated levels of hydroxybutyraldehyde, and these in turn are accompanied by an increased content of methylbutanediol and acetal.
  • increased butenediol levels not only lead to poor product quality, but also indicate a decreasing catalyst activity.
  • the liquid reaction mixture present in the reaction zone preferably has a butenediol content of at most 7000 ppm by weight.
  • control over the CO content in the exhaust gas In a first embodiment (variant 1), the content of the exhaust gas flow is measured in the method according to the invention and ensured by the measures described in more detail below, that the CO content does not exceed the specified limits.
  • a control of the production of 1, 4-butanediol by catalytic hydrogenation of 1, 4-butynediol at least with respect to at least one of the following properties: the activity of the catalyst,
  • the hydrogenation is carried out according to this variant at a temperature in the range of 100 to 300 ° C, more preferably from 100 to 200 ° C, in particular from 1 10 to 180 ° C.
  • the setpoint for the CO content in the exhaust gas is at most 5000 ppm by volume, more preferably at most 2000 ppm by volume, in particular at most 1000 ppm by volume and in particular at a maximum of 800 ppm by volume.
  • the setpoint for the CO content is preferably in a range from 0.05 to 5000 ppm by volume, more preferably in a range from 0.1 to 2000 ppm by volume, in particular in a range from 0.1 to 1000 ppm by volume and in particular in a range of 0.1 to 800 ppm by volume.
  • the limit value for the deviation of the actual value for the CO content in the exhaust gas from the desired value is preferably not more than 10%, particularly preferably not more than 5%, based on the desired value.
  • Typical CO contents in the exhaust gas of the catalytic hydrogenation of 1, 4-butynediol to produce 1, 4-butanediol initially in the hydrogenation with fresh catalyst are in a range of z. From 0.01 to 50 ppm. With increasing service life of the catalyst decreases the activity of the catalyst and increase the contents of CO in the exhaust gas usually slowly. Typical values for the increase in the CO content in the exhaust gas stream are about 1 to 50 ppm per day, depending on catalyst activity, catalyst age, load, temperature. In principle, it is difficult to keep the selectivity, the conversion and / or the product quality in the hydrogenation at an acceptable level even at high CO contents in the exhaust gas.
  • a removal of catalyst from the reaction zone is not carried out as a sole measure.
  • fresh catalyst is then fed to the reaction zone.
  • an increase in substrate loading per catalyst in the reaction zone can be avoided.
  • arbitrary frequent control interventions are possible until the CO content can no longer be kept in an acceptable range and z. B. the entire catalyst must be replaced.
  • the hydrogenation capacity can be measured in very short time intervals, ie. H. in minutes or even seconds. In any case, it can be ensured that the interval between two measurements is significantly less than the response time of the reaction system to a control intervention.
  • on-line measurement refers to a measurement which takes place without an extractive sampling and wherein the data are measured directly at the point of origin.
  • the volume ratio of CO: CO 2 is preferably not more than 1: 500, in particular 1: 400 and very particularly 1: 300.
  • the limit value for the deviation of the actual value for the CO content in the exhaust gas from the desired value is preferably not more than 10%, particularly preferably not more than 5%, based on the desired value. Preference is given to a method in which the content of the exhaust gas flow is measured by CO and, after reaching the limit value for the deviation of the actual value of the CO content of the exhaust gas flow from the target value, performs a control of at least one of the following parameters of the reaction zone.
  • An increase in the hydrogenation temperature is preferably carried out by 1 to 10 ° C, more preferably by 1 to 8 ° C, in particular by 1 to 5 ° C.
  • the energy introduced into the reaction zone is increased, it is preferably from 2 to 30%, more preferably from 2 to 20%, especially from 2 to 10%.
  • the increase in the energy input into the reaction zone can, for. B. by increasing the stirring energy, the enlisted by pumping in the circulating energy, the energy entered by gas injection energy, etc. take place.
  • fresh catalyst is fed into the reaction zone, it is preferably 1 to 50% by weight, preferably 1 to 30% by weight, in particular 1 to 10% by weight, of fresh catalyst, based on the total weight of the catalyst previously contained in the reaction zone ,
  • the amount of exhaust gas flow discharged from the reaction zone is increased, then preferably by 10 to 500 mol%, particularly preferably by 10 to 200 mol%, in particular by 10 to 100 mol%.
  • the pressure in the reaction zone is increased, then preferably by 1 to 30 bar, more preferably by 1 to 20 bar, in particular by 1 to 10 bar.
  • the content of the exhaust gas stream in CH 4 is measured in the method according to the invention and ensured by the measures described in more detail below that the CH content does not exceed the specified limits.
  • the content of CH 4 in the exhaust gas flow can be determined well by one of the measuring devices described above.
  • the measurement of the CH 4 content in the exhaust gas stream preferably takes place by means of an online IR measurement.
  • methane is not a catalyst poison, but a gas which is inert under the reaction conditions of the hydrogenation according to the invention.
  • the setpoint for the CH 4 content in the exhaust gas is preferably at most 15% by volume.
  • the target value for the CH 4 content in the exhaust gas is in a range from 1 to 15% by volume.
  • CH 4 content in the exhaust stream is dependent on which amounts of exhaust gas and in which excess the hydrogen is used in relation to the amount theoretically required for the hydrogenation of 1, 4-butynediol. So it is in principle also possible that the CH 4 content in the exhaust gas is more than 15 vol .-%, if this is compensated by a simultaneous increase in the hydrogen partial pressure.
  • the limit value for the deviation of the actual value for the CH 4 content in the exhaust gas from the desired value is at most 10%, particularly preferably at most 5%, based on the desired value.
  • Preference is given to a method in which the content of the exhaust gas flow to CH 4 is measured and after reaching the limit value for the deviation of the actual value of the CH 4 content the exhaust gas flow from the target value performs a control of at least one of the following parameters of the reaction zone:
  • a reduction in the hydrogenation temperature is preferably carried out by 1 to 10 ° C, more preferably by 1 to 8 ° C, in particular by 1 to 5 ° C.
  • catalyst from the reaction zone preferably 1 to 50% by weight, particularly preferably 1 to 30% by weight, in particular 1 to 10% by weight of the catalyst contained therein, based on the total weight of the catalyst present in the reaction mixture. zone contained catalyst.
  • the substrate loading per catalyst in kg (substrate) / (kg of catalyst) xh
  • the measures introduced in the context of the present invention can be used to control the hydrogenation and to keep at least one, preferably several, in particular all, of the aforementioned process parameters in the desired range.
  • the measures described herein can be taken to reduce the activity of the catalyst or to adjust the load, thereby decomposing less valuable product.
  • the measures described herein can be taken to increase or adjust the activity of the catalyst to maintain product quality.
  • the product quality of the crude 1,4-butanediol obtained by the process according to the invention is so high that post-hydrogenation is no longer necessary for many applications.
  • the measuring method used is an IR measurement.
  • the spectrometer is an IR spectrometer from the company Thermo Fisher type Protege 460.
  • the measuring cell is a 2 m multipass cell from Thermo Fisher. The measurement was carried out at room temperature. The evaluation for CO was carried out at 2175 cnr 1 , for CO2 at 2380 cnr 1 , for CH 4 at 3150 cm- 1 .
  • Example 1 (Measurement of the CO content and control by reduction of the substrate charge per catalyst) A 2 l autoclave with a fill level of 1 l was charged with 100 g of Raney nickel molybdenum catalyst and heated to 160 ° C. with stirring and 45 bar H2 pressed on. An aqueous about 50 wt -.% Butynediol solution was driven at a feed rate of 800 to 1000 g (butynediol solution) / h in the autoclave and discharged a correspondingly high product flow from the reactor. The h-feed corresponded to about 2.2 moles of H2 per mole of butynediol.
  • Example 2 (hydrogenation of butynediol, measurement of CH 4 content and control by reducing the hydrogenation temperature)
  • the reaction conditions correspond to those of Example 1.
  • the butynediol feed was 900 g (butynediol solution) / h.
  • the amount of methane in the exhaust was 30% by volume, while the CO content in the exhaust gas was 0.1 ppm.
  • the propanol content in the product was 2%.
  • the methane content in the exhaust gas could be reduced to 15% by volume.
  • the propanol content in the product fell to 1, 5%, so that the butanediol content rose from 95 to 95.5%.
  • the remainder consisted essentially of methanol (formaldehyde), butanol, GBL and other by-products.
  • the reaction conditions correspond to those of Example 2.
  • the butynediol feed was 900 g (butynediol solution) / h at a temperature of 150 ° C.
  • the CO content in the exhaust gas increased from 0.1 ppm to 170 ppm in the exhaust gas, while the CHU content dropped from 15% by volume to 11% by volume.
  • the content of butenediol increased from ⁇ 5 ppm to 140 ppm and the acetal content increased from 300 ppm to 600 ppm in the discharge.
  • the temperature was raised from 150 ° C to 152 ° C, the content of CO in the exhaust gas dropped from 170 ppm to 30 ppm, while the methane content dropped from 1 to 1% by volume
  • the reaction conditions correspond to those of Example 3.
  • the butynediol feed was 900 g (butynediol solution) / h.
  • the limit of 170 ppm of CO in the exhaust gas was again exceeded at a temperature of 160 ° C.
  • 10 g of the spent catalyst were discharged via a lock and 10 g of fresh catalyst added to the system.
  • the CO content in the exhaust gas dropped from 170 ppm to 27 ppm and the butenediol content in the exhaust dropped from 120 ppm to 19 ppm, while the acetal content dropped from 780 ppm to 326 ppm.
  • the methane content increased after the catalyst introduction of 7 vol% to 8.2 vol%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production de 1,4-butanediol par hydrogénation catalytique de 1,4-butynediol dans une zone de réaction avec de l'hydrogène en présence d'un catalyseur d'hydrogénation hétérogène. Selon ce procédé, on mesure la teneur du flux de gaz résiduaires en au moins un gaz, choisi parmi le CO et le CH4, et on utilise la teneur du flux de gaz résiduaires en gaz mesuré pour réguler l'hydrogénation.
EP18758629.2A 2017-09-06 2018-08-27 Procédé pour réguler l'hydrogénation catalytique de 1,4-butynediol par l'intermédiaire de la teneur en co et/ou ch4 du flux de gaz résiduaires Withdrawn EP3679006A1 (fr)

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EP17189578 2017-09-06
PCT/EP2018/072999 WO2019048276A1 (fr) 2017-09-06 2018-08-27 Procédé pour réguler l'hydrogénation catalytique de 1,4-butynediol par l'intermédiaire de la teneur en co et/ou ch4 du flux de gaz résiduaires

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Publication number Priority date Publication date Assignee Title
US1563587A (en) 1924-09-20 1925-12-01 Raney Murray Method of preparing catalytic material
US1628190A (en) 1926-05-14 1927-05-10 Raney Murray Method of producing finely-divided nickel
US1915473A (en) 1930-12-31 1933-06-27 Raney Murray Method of preparing catalytic material
DE1285992B (de) 1966-06-29 1969-01-02 Basf Ag Verfahren zur Herstellung von gesaettigten Alkoholen durch Hydrierung von Alkinolen und Alkindiolen
US3449445A (en) 1967-03-17 1969-06-10 Gaf Corp Process of preparing 1,4-butanediol
CA922738A (en) * 1969-01-31 1973-03-13 G. Low Frederick Hydrogenation of aqueous butynediol over a nickel-aluminum catalyst
DE2619660A1 (de) 1975-05-05 1976-11-18 Gaf Corp Verfahren zur herstellung von butendiol
DE2536273C2 (de) 1975-08-14 1986-01-02 Basf Ag, 6700 Ludwigshafen Katalysator zur Hydrierung von Acetylenalkoholen
US4361495A (en) 1981-03-13 1982-11-30 Gaf Corporation Regeneration of supported-nickel catalysts
CA1146148A (fr) 1981-06-30 1983-05-10 James Den Hartog Module de catalyse a lits de densites ordonnees
DE3561879D1 (en) 1984-10-12 1988-04-21 Basf Ag Process for the production of alkane diols
DE3513726A1 (de) 1985-04-17 1986-10-23 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von katalysatoren fuer die abgasentgiftung
DE3574937D1 (de) 1985-05-14 1990-02-01 Sulzer Ag Reaktor zum durchfuehren von heterogenen, katalysierten chemischen reaktionen.
DD265396A1 (de) 1986-04-16 1989-03-01 Leuna Werke Veb Verfahren zur herstellung von butandiol-1,4
DE3913839A1 (de) 1989-04-27 1990-10-31 Basf Ag Verfahren zur hydrierung von acetylenalkoholen
DE3913835A1 (de) 1989-04-27 1990-10-31 Basf Ag Katalysator fuer die hydrierung aliphatischer ungesaettigter verbindungen
EP0448884B1 (fr) 1990-03-30 1995-05-24 Koch Engineering Company Inc Structure et procédé catalytique de réaction entre des courants fluides dans un dispositif de transfert de masse
US5068468A (en) 1990-10-19 1991-11-26 Basf Aktiengesellschaft Hydrogenation of acetylenic alcohols
DE19641707A1 (de) 1996-10-10 1998-04-16 Basf Ag Verfahren zur Herstellung von 1,4-Butandiol durch katalytische Hydrierung von 1,4-Butindiol
DE19755347A1 (de) 1997-12-12 1999-06-17 Basf Ag Verfahren zur Hydrierung von Alkinolen unter Verwendung eines Makroporen aufweisenden Katalysators
EP3216522A1 (fr) 2013-02-06 2017-09-13 Alantum Europe GmbH Corps en mousse métallique à surface modifiée, son procédé de production et son utilisation

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CN111094222A (zh) 2020-05-01
US20200207690A1 (en) 2020-07-02
JP2020532566A (ja) 2020-11-12
WO2019048276A1 (fr) 2019-03-14
TW201914986A (zh) 2019-04-16

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