EP1444185A2 - Method for catalytic production of methanol and a device for implementing said method - Google Patents

Method for catalytic production of methanol and a device for implementing said method

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Publication number
EP1444185A2
EP1444185A2 EP02782960A EP02782960A EP1444185A2 EP 1444185 A2 EP1444185 A2 EP 1444185A2 EP 02782960 A EP02782960 A EP 02782960A EP 02782960 A EP02782960 A EP 02782960A EP 1444185 A2 EP1444185 A2 EP 1444185A2
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EP
European Patent Office
Prior art keywords
methanol
absorption
synthesis
production
catalytic
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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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EP02782960A
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German (de)
French (fr)
Inventor
Hans-Joachim Bähnisch
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ThyssenKrupp Industrial Solutions AG
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Uhde GmbH
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Publication of EP1444185A2 publication Critical patent/EP1444185A2/en
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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
    • C07C29/152—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 characterised by the reactor used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a method for catalytic methanol production and an apparatus for performing the method. Similar processes for the catalytic production of methanol have long been known, examples of which are the publications DE 21 17 060, DE 25 29 591, DE 32 20 995, DE 35 18 362, US 29 04 575 and DE 41 00 for the abundance of solutions 632 are mentioned.
  • a suitable synthesis gas which essentially contains the components carbon monoxide, carbon dioxide and hydrogen, but also small amounts of other components, such as water vapor, nitrogen, methane, ammonia, ethene, ethyne, hydrogen cyanide, oxygen , Sulfur compounds, chlorine compounds, iron compounds, in particular iron carbonyls, elemental carbon, in particular soot particles, metal compounds of the metals vanadium, potassium, sodium and nickel, and solid particles as dust.
  • This synthesis gas is usually passed at a pressure of approximately 40 to 100 bar into a reaction system of several cascade-like and / or in a circuit system, in which there is usually a catalyst bed and a device for heat dissipation.
  • catalysts special copper-containing catalysts are used, but which has the disadvantage that they are very expensive, are very sensitive to catalyst poisons, that secondary reactions occur at high temperatures, in which ethanol, butanol and dimethyl ether form, and also, that at relatively high operating temperatures a rearrangement of the catalytically active copper crystallites to larger crystals with a smaller specific surface occurs, which reduces the space-specific activity of the catalyst.
  • the catalyst layers closest to the synthesis gas entry are increasingly poisoned by the catalyst poisons present in traces.
  • the poisoning occurs in different ways: On the one hand, sulfur and chlorine compounds and ammonia chemically inactivate the catalytically active catalyst components. Solid particles also occupy the surface of the catalyst and form a layer which prevents diffusion.
  • iron and nickel carbonyl compounds as well as other metal compounds which e.g. can be removed from the pipe material or other construction materials of the plant by corrosion (rust) or abrasion, change the catalytic system as such and contribute to the catalysis of other undesired end products. Since all of these poisonings are irreversible, the entire catalyst must be disposed of after use and cannot be regenerated.
  • the operator can first react to the increasing poisoning by increasing the partial pressures of the components involved in the reaction, then by increasing the total pressure, which in turn requires increased compression effort, and finally by increasing the reaction temperature by increasing pressure and temperature of the moderating steam can be increased.
  • the last measure would accelerate the aging process of the not poisoned portion of the catalyst mass and lead to the known and undesirable by-products. Therefore, there has long been a considerable interest in the system planners and the system operators in solving this problem.
  • the object of the invention is therefore to overcome the known problems with an economical solution.
  • the invention achieves the object in that each catalytic reaction system for the production of methanol is preceded by an absorption stage which contains as the absorption medium catalyst material which is suitable for the synthesis of methanol, and which absorption stage is operated at a temperature which is below that for the catalytic conversion to methanol.
  • the mode of operation of this absorption device is that the catalyst poisons, which would poison the subsequent catalyst in which the methanol synthesis is carried out, are instead deposited on the upstream catalyst material and are thus absorptively deposited.
  • This has the advantage that the subsequent catalyst is not poisoned and that there is no need for the plant planner to make generous safety surcharges when designing the required catalyst volume in the reactor of the methanol synthesis.
  • the requirements for the other synthesis gas cleaning also decrease accordingly, the person skilled in the art weighing up the effort of the absorption device and that for the other synthesis gas cleaning.
  • the absorption device can be carried out in a simple manner, since no devices for heat dissipation as in methanol synthesis reactors are required, and it can be designed as a simple cylindrical container with internals for holding the bed while it is being flowed through in the axial or radial direction, furthermore, each with end openings for the gas inlet and outlet, and the possibility of filling or removing catalyst material. It is advantageous to use 2 containers connected in parallel, each of which can be individually shut off on the gas side, so that the catalyst material can be filled or emptied so that it is also possible to change the absorption material during operation.
  • the absorption device should be arranged as close as possible to the synthesis reactor, preferably both devices are separated from one another only by a heat exchanger which raises the temperature of the synthesis gas to the synthesis level. Furthermore, it is also possible to arrange the absorption device before or after the compression stage, which generates the pressure required for the methanol synthesis, this can be particularly useful in a plant with a large number of reactors for the methanol synthesis.
  • Combinations of these two arrangement options can be expedient, in particular if external gas flows caused by the synthesis gas after the synthesis gas are involved
  • compression is still admixed by the synthesis reactors, furthermore if, due to the choice of construction materials, corrosion with the result of metal detachments between the compression and the methanol reactors is to be expected.
  • FIG. 1 shows the use of the process according to the invention within a circulatory plant for the production of methanol with a synthetic heat transfer system, an absorption device and a Reactor for methanol synthesis with integrated steam generation.
  • the production, dewatering and pre-cleaning of the synthesis gas and the compression to the synthesis pressure are not shown, furthermore the necessary cleaning steps for the methanol produced.
  • the cycle synthesis gas 1 is mixed into the cycle synthesis gas 2, which then has a temperature of about 77 ° C.
  • the cycle synthesis gas is heated to approximately 160 ° C. and then introduced into the absorption device 4.
  • this absorption device 4 consists of the two bulk material containers 5 and 6, which contain the catalyst filling according to the invention. While the bulk synthesis container 5 is flowed through from the cycle synthesis gas from top to bottom and the catalyst poisons contained in the cycle synthesis gas combine with the catalyst filling and are thus absorbed, the bulk material container 6 also filled with catalyst filling is not flowed through, represented by shut-off valves downstream, kept in reserve.
  • the cleaned cycle synthesis gas 7 is passed into the heat exchanger s at substantially unchanged temperature, heated there to the synthesis temperature of approx. 220 ° C., and then introduced directly into the reactor for methanol synthesis 9. This is where the catalytic conversion to methanol takes place, which is gaseous at this temperature and synthesis pressure.
  • the considerable heat of reaction is given off to the boiler feed water 10, which flows through the reactor, for example, on the jacket side, steam 11 being produced.
  • the methanol concentration in the remaining synthesis gas 12 is usually about 4 to 10 mol%.
  • This methanol-containing synthesis gas 12 is first cooled against the cycle synthesis gas in the heat exchangers 8 and 3.
  • the gaseous methanol is condensed out in the condenser 13 and separated from the remaining synthesis gas 16 in the methanol separator 14 and obtained as crude methanol 15.
  • the remaining synthesis gas 16 is partly recompressed by the circulating gas compressor 17 as recycle synthesis gas and returned to the synthesis circuit and partly discharged as purge gas from the synthesis circuit in order to prevent it from being enriched with inert constituents.

Abstract

The invention relates to a method for the catalytic production of methanol under pressure from a synthesis gas, which contains at least hydrogen, carbon monoxide, carbon dioxide and undesirable impurities, by means of at least one stage provided with a reactor. According to said invention, an absorption stage precedes each catalytic reaction system for producing methanol. Said absorption stage contains a catalyst material as an absorbent, which is suitable for the methanol synthesis, and operates at a temperature below the catalytic reaction temperature for the methanol production.

Description

Verfahren zur katalytischen Methanolherstellung sowie Vorrichtung zur Durchführung des Verfahrens Process for the catalytic production of methanol and device for carrying out the process
[0001] Die Erfindung betrifft ein Verfahren zur katalytischen Methanolherstellung sowie eine Vorrichtung zur Durchführung des Verfahrens. Ähnliche Verfahren zur katalytischen Methanolherstellung sind bereits seit langem bekannt, wobei für die Fülle der Lösungen hier als Beispiele die Schriften DE 21 17 060, DE 25 29 591 , DE 32 20 995, DE 35 18 362, US 29 04 575 und DE 41 00 632 genannt seien.The invention relates to a method for catalytic methanol production and an apparatus for performing the method. Similar processes for the catalytic production of methanol have long been known, examples of which are the publications DE 21 17 060, DE 25 29 591, DE 32 20 995, DE 35 18 362, US 29 04 575 and DE 41 00 for the abundance of solutions 632 are mentioned.
[0002] Bei Technologien dieser Art wird üblicherweise ein geeignetes Synthesegas verwendet, welches im Wesentlichen die Komponenten Kohlenmonoxid, Kohlendioxid und Wasserstoff enthält, aber auch geringe Mengen von anderen Komponenten, wie Wasserdampf, Stickstoff, Methan, Ammoniak, Ethen, Ethin, Cyanwasserstoff, Sauerstoff, Schwefelverbindungen, Chlorverbindungen, Eisenverbindungen, insbesondere Eisencarbonyle, Elementarkohlenstoff, insbesondere Rußpartikel, Metallverbindungen der Metalle Vanadium, Kalium, Natrium und Nickel, sowie Feststoffpartikel als Staub. Dieses Synthesegas wird üblicherweise bei einem Druck von ca. 40 bis 100 bar in ein Reaktionssystem von mehreren kaskadenartig und/oder in einem Kreislaufsystem angeordneten Reaktoren geleitet, in denen sich in der Regel eine Katalysatorschüttung und eine Einrichtung zur Wärmeabfuhr befindet. In jedem der Reaktoren erfolgt oberhalb von 200°C jeweils eine Teilumsetzung zu Methanol, welches im Anschluss an die jeweiligen Reaktoren auskondensiert und gereinigt wird. Die bei der Umsetzung in der Katalysatorschicht der Reaktoren freiwerdende Reaktionswärme wird zur Produktion von Dampf genutzt, der anderweitig genutzt werden kann, zu diesem Zweck sind in der Katalysatorschicht Rohrbündel angeordnet, die mit Kesselspeisewasser beschickt werden, welches in diesen Rohrleitungen verdampft.In technologies of this type, a suitable synthesis gas is usually used, which essentially contains the components carbon monoxide, carbon dioxide and hydrogen, but also small amounts of other components, such as water vapor, nitrogen, methane, ammonia, ethene, ethyne, hydrogen cyanide, oxygen , Sulfur compounds, chlorine compounds, iron compounds, in particular iron carbonyls, elemental carbon, in particular soot particles, metal compounds of the metals vanadium, potassium, sodium and nickel, and solid particles as dust. This synthesis gas is usually passed at a pressure of approximately 40 to 100 bar into a reaction system of several cascade-like and / or in a circuit system, in which there is usually a catalyst bed and a device for heat dissipation. In each of the reactors, partial conversion to methanol takes place above 200 ° C., which is condensed out and purified after the respective reactors. The reaction heat released in the reaction in the catalyst layer of the reactors is used to produce steam that can be used for other purposes. For this purpose, tube bundles are arranged in the catalyst layer, which are fed with boiler feed water, which evaporates in these pipes.
[0003] Als Katalysatoren werden spezielle kupferhaltige Katalysatoren verwendet, an denen jedoch nachteilig ist, dass sie sehr teuer sind, sehr empfindlich gegenüber Katalysatorgiften sind, dass bei hohen Temperaturen vermehrt Nebenreaktionen auftreten, bei denen sich Ethanol, Butanol und Dimethylether bilden, und außerdem, dass bei relativ hohen Betriebstemperaturen eine Umlagerung der katalytisch wirkenden Kupferkristallite hin zu größeren Kristallen mit geringerer spezifischer Oberfläche auftritt, was die raumspezifische Aktivität des Katalysators herabsetzt.As catalysts, special copper-containing catalysts are used, but which has the disadvantage that they are very expensive, are very sensitive to catalyst poisons, that secondary reactions occur at high temperatures, in which ethanol, butanol and dimethyl ether form, and also, that at relatively high operating temperatures a rearrangement of the catalytically active copper crystallites to larger crystals with a smaller specific surface occurs, which reduces the space-specific activity of the catalyst.
[0004] Die Planer von Anlagen zur Herstellung von Methanol sehen sich daher mit dem Problem konfrontiert, durch ausreichende Dimensionierung des Katalysatorvolumens und aufwändige Entfernung von Katalysatorgiften im Synthesegas lange Stand- Zeiten der Reaktoren für die Nennleistung der Methanolherstellungskapazität sicherzustellen. Dies geschieht in der Regel durch großzügige Sicherheitszuschläge bei der Auslegung des erforderlichen Katalysatorvolumens, was die spezifischen Investitionskosten entsprechend erhöht.[0004] The planners of plants for the production of methanol are therefore faced with the problem of long standing by adequate dimensioning of the catalyst volume and complex removal of catalyst poisons in the synthesis gas. Ensure times of reactors for the nominal capacity of the methanol manufacturing capacity. This is usually done through generous safety supplements when designing the required catalyst volume, which increases the specific investment costs accordingly.
[0005] Die Betreiber von Anlagen zur Herstellung von Methanol sehen sich in der Folge mit dem Problem konfrontiert, dass die Aktivität über die Lebensdauer des Katalysators starken Schwankungen unterworfen ist. Zu Beginn eines Produktionszyklusses ist neu eingefülltes Katalysatormaterial besonders aktiv, weswegen ständig gegen die Gefahr durchgehender Reaktionen angekämpft werden muss, etwa indem die Dampfproduktion, die die Reaktion moderiert, bei geringerer Temperatur und geringerem Druck betrieben wird, was eine Verringerung der Dampfqualität zur Folge hat. Eine andere Möglichkeit besteht darin, das Synthesegas mit inerten Komponenten entsprechend zu verdünnen, nachteilig daran ist aber der damit verbundene erhöhte Aufwand für die Verdichtung. Würde die Methanolsynthese ungedämpft ablaufen, stiegen die Temperaturen in den Reaktoren in einer Weise, dass erhöhte Nebenproduktbildung und eine schnellere Alterung des Katalysators durch Kristallitumbildung die Folge wäre.The operators of plants for the production of methanol are subsequently faced with the problem that the activity is subject to strong fluctuations over the life of the catalyst. At the beginning of a production cycle, newly filled catalyst material is particularly active, which is why it is necessary to constantly fight against the risk of continuous reactions, for example by operating the steam production that moderates the reaction at a lower temperature and pressure, which results in a reduction in the steam quality. Another possibility is to correspondingly dilute the synthesis gas with inert components, but the disadvantage of this is the increased outlay for compression associated with this. If the methanol synthesis were to proceed undamped, the temperatures in the reactors would rise in such a way that increased by-product formation and a faster aging of the catalyst due to crystallite formation would result.
[0006] Im weiteren Verlauf des Produktionszyklusses werden die dem Synthese- gaseintritt am nächsten liegenden Katalysatorschichten durch die in Spuren vorhandenen Katalysatorgifte zunehmend vergiftet. Die Vergiftung geschieht dabei auf verschiedene Weise: Zum einen inaktivieren Schwefel- und Chlorverbindungen sowie Ammoniak die katalytisch aktiven Katalysatorkomponenten chemisch. Weiterhin belegen Feststoffpartikel die Oberfläche des Katalysators und bilden eine die Diffusion behin- dernde Schicht aus. Im Übrigen können Eisen- und Nickelcarbonylverbindungen sowie weitere Metallverbindungen, welche z.B. aus dem Rohrmaterial oder anderen Konstruktionsmaterialien der Anlage durch Korrosion (Rost) oder Abrieb herausgelöst werden, das katalytische System als solches verändern und zur Katalyse anderer unerwünschter Endprodukte beitragen. Da alle diese Vergiftungen irreversibel sind, muss der gesamte Katalysator nach seinem Gebrauch entsorgt werden und kann nicht regeneriert werden.[0006] In the further course of the production cycle, the catalyst layers closest to the synthesis gas entry are increasingly poisoned by the catalyst poisons present in traces. The poisoning occurs in different ways: On the one hand, sulfur and chlorine compounds and ammonia chemically inactivate the catalytically active catalyst components. Solid particles also occupy the surface of the catalyst and form a layer which prevents diffusion. Incidentally, iron and nickel carbonyl compounds as well as other metal compounds, which e.g. can be removed from the pipe material or other construction materials of the plant by corrosion (rust) or abrasion, change the catalytic system as such and contribute to the catalysis of other undesired end products. Since all of these poisonings are irreversible, the entire catalyst must be disposed of after use and cannot be regenerated.
[0007] Der Betreiber kann auf die zunehmende Vergiftung zunächst mit einer Anhebung der Partialdrücke der an der Reaktion beteiligten Komponenten reagieren, so- dann mit einer Anhebung des Gesamtdruckes, was wiederum erhöhten Verdichtungsaufwand erfordert, und als letztes mit einer Erhöhung der Reaktionstemperatur, indem Druck und Temperatur des moderierenden Dampfes erhöht werden. Die letzte Maß- nähme beschleunigt jedoch den Alterungsprozess des noch nicht vergifteten Anteils an Katalysatormasse und führt zu den bekannten und unerwünschten Nebenprodukten. Es besteht daher seit langem ein erhebliches Interesse der Anlagenplaner und der Anlagenbetreiber an einer Lösung dieser Problematik.[0007] The operator can first react to the increasing poisoning by increasing the partial pressures of the components involved in the reaction, then by increasing the total pressure, which in turn requires increased compression effort, and finally by increasing the reaction temperature by increasing pressure and temperature of the moderating steam can be increased. The last measure would accelerate the aging process of the not poisoned portion of the catalyst mass and lead to the known and undesirable by-products. Therefore, there has long been a considerable interest in the system planners and the system operators in solving this problem.
[0008] Die Aufgabe der Erfindung besteht daher darin, mit einer wirtschaftlichen Lösung die bekannten Probleme zu überwinden.The object of the invention is therefore to overcome the known problems with an economical solution.
[0009] Die Erfindung löst die Aufgabe dadurch, dass jedem katalytischen Reakti- onssystem zur Herstellung von Methanol eine Absorptionsstufe vorgeschaltet wird, welche als Absorptionsmittel Katalysatormaterial enthält, welches für die Synthese von Methanol tauglich ist, und welche Absorptionsstufe bei einer Temperatur betrieben wird, die unterhalb der für die katalytische Umsetzung zu Methanol liegt.[0009] The invention achieves the object in that each catalytic reaction system for the production of methanol is preceded by an absorption stage which contains as the absorption medium catalyst material which is suitable for the synthesis of methanol, and which absorption stage is operated at a temperature which is below that for the catalytic conversion to methanol.
[0010] Die Wirkungsweise dieser Absorptionsvorrichtung besteht darin, dass sich die Katalysatorgifte, die den nachfolgenden Katalysator, in dem die Methanolsynthese durchgeführt wird, vergiften würden, statt dessen auf dem vorgeschalteten Katalysatormaterial niederschlagen und somit absorptiv abgeschieden werden. Dies hat den Vorteil, dass der nachfolgende Katalysator nicht vergiftet wird und sich für den Anla- genplaner keine Notwendigkeit ergibt, großzügige Sicherheitszuschläge bei der Auslegung des erforderlichen Katalysatorvolumens im Reaktor der Methanolsynthese vorzunehmen. Auch sinken entsprechend die Anforderungen an die sonstige Synthesegasreinigung, wobei der Fachmann zwischen dem Aufwand der Absorptionseinrichtung und dem für die sonstige Synthesegasreinigung abwägen wird.The mode of operation of this absorption device is that the catalyst poisons, which would poison the subsequent catalyst in which the methanol synthesis is carried out, are instead deposited on the upstream catalyst material and are thus absorptively deposited. This has the advantage that the subsequent catalyst is not poisoned and that there is no need for the plant planner to make generous safety surcharges when designing the required catalyst volume in the reactor of the methanol synthesis. The requirements for the other synthesis gas cleaning also decrease accordingly, the person skilled in the art weighing up the effort of the absorption device and that for the other synthesis gas cleaning.
[0011] Für den Anlagenbetreiber ergibt sich dadurch eine sehr viel gleichmäßigere und wirtschaftlichere Fahrweise über die gesamte Katalysatorstandzeit der Methanolsynthesereaktoren, wobei sich die Katalysatorstandzeit dadurch auch erheblich verlängert.For the plant operator, this results in a much more uniform and economical operation over the entire catalyst life of the methanol synthesis reactors, the catalyst life also being extended considerably as a result.
[0012] Da an das als Absorptionsmittel verwendete Katalysatormaterial keine Anforderungen an die Selektivität der Umsätze gestellt werden, es finden ja im Idealfall überhaupt keine Umsätze statt, kann als Absorptionsmaterial auch besonders preiswertes Katalysatormaterial, etwa solches der Zusammensetzung 30 bis 50 % CuO, 30 bis 50 % ZnO und 10 bis 30 % AI2O3, eingesetzt werden, was ein weiterer Vorteil der Erfindung ist. [0013] Bei der Wahl der Betriebstemperatur der Absorptionseinrichtung ist lediglich darauf zu achten, dass einerseits die Vergiftungsreaktionen stattfinden können, andererseits aber ein Zünden der Methanolsynthesereaktion sicher ausbleibt. Hierzu wird eine Temperatur »zwischen 100 CC und 200 °C eingestellt, vorzugsweise beträgt die Absorptionstemperatur 150 CC.Since no requirements are placed on the selectivity of the sales to the catalyst material used as an absorbent, ideally there are no sales at all, particularly inexpensive catalyst material, such as those of the composition 30 to 50% CuO, 30 to, can be used as the absorption material 50% ZnO and 10 to 30% Al 2 O 3 can be used, which is a further advantage of the invention. When choosing the operating temperature of the absorption device, it is only necessary to ensure that, on the one hand, the poisoning reactions can take place, but on the other hand that the methanol synthesis reaction does not ignite reliably. For this purpose, a temperature "is between 100 C C and 200 ° C is set, preferably the absorption temperature 150 C C.
[0014] Die Absorptionseinrichtung kann in einfacher Weise ausgeführt werden, da keine Einrichtungen zur Wärmeabfuhr wie in Methanolsynthesereaktoren erforderlich sind, wobei sie als einfacher zylindrischer Behälter mit Einbauten zum Festhalten der Schüttung, während sie in axialer oder radialer Richtung durchströmt wird, ausgebildet werden kann, ferner mit jeweils stirnseitigen Öffnungen für den Gaseintritt und -austritt, sowie der Möglichkeit, Katalysatormaterial einzufüllen oder zu entnehmen. Vorteilhaft ist der Einsatz von 2 parallel geschalteten Behältern, die jeweils einzeln gasseitig absperrbar sind, so dass eine Füllung oder Entleerung von Katalysatormaterial möglich ist, damit es auch im laufenden Betrieb möglich ist, das Absorptionsmaterial zu wechseln.The absorption device can be carried out in a simple manner, since no devices for heat dissipation as in methanol synthesis reactors are required, and it can be designed as a simple cylindrical container with internals for holding the bed while it is being flowed through in the axial or radial direction, furthermore, each with end openings for the gas inlet and outlet, and the possibility of filling or removing catalyst material. It is advantageous to use 2 containers connected in parallel, each of which can be individually shut off on the gas side, so that the catalyst material can be filled or emptied so that it is also possible to change the absorption material during operation.
[0015] Die Absorptionseinrichtung sollte so nah wie möglich am Synthesereaktor angeordnet sein, vorzugsweise sind beide Einrichtungen nur durch einen Wärmetau- scher, welcher die Temperatur des Synthesegases auf Syntheseniveau anhebt, von einander getrennt. Weiterhin ist aber auch möglich, die Absorptionseinrichtung vor oder nach der Verdichtungsstufe, die den für die Methanolsynthese erforderlichen Druck erzeugt, anzuordnen, dies kann insbesondere in einer Anlage mit einer großen Anzahl von Reaktoren für die Methanolsynthese sinnvoll sein. Auch Kombinationen dieser bei- den Anordnungsmöglichkeiten, wobei zunächst eine zentrale Absorptionseinrichtung die Hauptlast an Katalysatorvergiftem absorbiert und jeweils vor den einzelnen Methanolreaktoren noch zur Sicherheit weitere Absorptionseinrichtungen angeordnet sind, können sinnvoll sein, insbesondere dann, wenn durch die Anlageneinbindung bedingt externe Gasströme dem Synthesegas nach der Verdichtung aber noch von den Syn- thesereaktoren zugemischt werden, ferner dann, wenn, bedingt durch die Wahl der Konstruktionsmaterialien, Korrosion mit der Folge von Metallablösungen zwischen der Verdichtung und den Methanolreaktoren zu erwarten ist.[0015] The absorption device should be arranged as close as possible to the synthesis reactor, preferably both devices are separated from one another only by a heat exchanger which raises the temperature of the synthesis gas to the synthesis level. Furthermore, it is also possible to arrange the absorption device before or after the compression stage, which generates the pressure required for the methanol synthesis, this can be particularly useful in a plant with a large number of reactors for the methanol synthesis. Combinations of these two arrangement options, with a central absorption device initially absorbing the main load of catalyst poisoning and additional absorption devices being arranged in front of the individual methanol reactors for safety reasons, can be expedient, in particular if external gas flows caused by the synthesis gas after the synthesis gas are involved However, compression is still admixed by the synthesis reactors, furthermore if, due to the choice of construction materials, corrosion with the result of metal detachments between the compression and the methanol reactors is to be expected.
[0016] Die Erfindung wird nachfolgend anhand eines Verfahrensschemas in Fig. 1 näher erläutert: Fig. 1 zeigt den Einsatz des erfindungsgemäßen Verfahrens innerhalb einer im Kreislauf betriebenen Anlage zur Herstellung von Methanol mit einem synthe- segasseitigen Wärmeverschiebungssystem, einer Absorptionsvorrichtung und einem Reaktor zur Methanolsynthese mit integrierter Dampfgewinnung. Nicht dargestellt sind die Herstellung, Entwässerung und Vorreinigung des Synthesegases sowie die Verdichtung auf den Synthesedruck, ferner die erforderlichen Reinigungsschritte für das erzeugte Methanol.[0016] The invention is explained in more detail below with reference to a process scheme in FIG. 1: FIG. 1 shows the use of the process according to the invention within a circulatory plant for the production of methanol with a synthetic heat transfer system, an absorption device and a Reactor for methanol synthesis with integrated steam generation. The production, dewatering and pre-cleaning of the synthesis gas and the compression to the synthesis pressure are not shown, furthermore the necessary cleaning steps for the methanol produced.
[0017] Vorverdichtetes, frisches Synthesegas 1 wird dem Kreislauf-Synthesegas 2 zugemischt, welches danach eine Temperatur von etwa 77 °C aufweist. Im Wärmetauscher 3 wird das Kreislauf-Synthesegas auf ca. 160 °C aufgeheizt und danach in die Absorptionsvorrichtung 4 eingeleitet. Diese Absorptionsvorrichtung 4 besteht in diesem Beispiel aus den beiden Schüttgutbehältern 5 und 6, welche die erfindungsgemäße Katalysatorfüllung enthalten. Während der Schüttgutbehälter 5 vom Kreislauf-Synthesegas von oben nach unten durchströmt wird und sich die im Kreislauf-Synthesegas enthaltenen Katalysatorgifte mit der Katalysatorfüllung verbinden und somit absorbiert werden, wird der ebenfalls mit Katalysatorfüllung befüllte Schüttgutbehälter 6 undurch- strömt, dargestellt durch Absperrventile zu- und abströmseitig, in Reserve gehalten. Das gereinigte Kreislauf-Synthesegas 7 wird bei im wesentlichen unveränderter Temperatur in den Wärmetauscher s geleitet, dort auf die Synthesetemperatur von ca. 220°C aufgeheizt, und danach unmittelbar in den Reaktor zur Methanolsynthese 9 eingeleitet. Dort findet die katalytische Umsetzung zu Methanol statt, welches bei dieser Temperatur und Synthesedruck gasförmig vorliegt. Die erhebliche Reaktionswärme wird dabei an das Kesselspeisewasser 10, welches z.B. mantelseitig den Reaktor durchströmt, abgegeben, wobei Dampf 11 produziert wird. Üblicherweise beträgt die Methanol-Konzentration im verbleibenden Synthesegas 12 etwa 4 bis 10 Mol-%. Dieses methanolhaltige Synthesegas 12 wird zunächst gegen das Kreislauf-Synthesegas in den Wärmetauschern 8 und 3 abgekühlt. Daran anschließend wird das gasförmige Methanol im Kondensator 13 auskondensiert und im Methanolabscheider 14 vom verbleibenden Synthesegas 16 getrennt und als Rohmethanol 15 gewonnen. Das verbleibende Synthesegas 16 wird zum einen Teil vom Kreisgasverdichter 17 rückverdichtet als Kreislauf-Synthesegas in den Synthesekreislauf zurückgeführt und zum an- deren Teil als Spülgas aus dem Synthesekreislauf ausgeschleust, um eine Anreicherung mit inerten Bestandteilen zu unterbinden. BezugszeichenlistePre-compressed, fresh synthesis gas 1 is mixed into the cycle synthesis gas 2, which then has a temperature of about 77 ° C. In the heat exchanger 3, the cycle synthesis gas is heated to approximately 160 ° C. and then introduced into the absorption device 4. In this example, this absorption device 4 consists of the two bulk material containers 5 and 6, which contain the catalyst filling according to the invention. While the bulk synthesis container 5 is flowed through from the cycle synthesis gas from top to bottom and the catalyst poisons contained in the cycle synthesis gas combine with the catalyst filling and are thus absorbed, the bulk material container 6 also filled with catalyst filling is not flowed through, represented by shut-off valves downstream, kept in reserve. The cleaned cycle synthesis gas 7 is passed into the heat exchanger s at substantially unchanged temperature, heated there to the synthesis temperature of approx. 220 ° C., and then introduced directly into the reactor for methanol synthesis 9. This is where the catalytic conversion to methanol takes place, which is gaseous at this temperature and synthesis pressure. The considerable heat of reaction is given off to the boiler feed water 10, which flows through the reactor, for example, on the jacket side, steam 11 being produced. The methanol concentration in the remaining synthesis gas 12 is usually about 4 to 10 mol%. This methanol-containing synthesis gas 12 is first cooled against the cycle synthesis gas in the heat exchangers 8 and 3. Subsequently, the gaseous methanol is condensed out in the condenser 13 and separated from the remaining synthesis gas 16 in the methanol separator 14 and obtained as crude methanol 15. The remaining synthesis gas 16 is partly recompressed by the circulating gas compressor 17 as recycle synthesis gas and returned to the synthesis circuit and partly discharged as purge gas from the synthesis circuit in order to prevent it from being enriched with inert constituents. LIST OF REFERENCE NUMBERS
1 frisches Synthesegas1 fresh synthesis gas
2 Kreislauf-Synthesegas2 cycle synthesis gas
3 Wärmetauscher3 heat exchangers
4 Absorptionseinrichtung4 absorption device
5 Schüttgutbehälter5 bulk containers
6. Schüttgutbehälter6. Bulk goods container
7 gereinigtes Synthesegas7 purified synthesis gas
8 Wärmetauscher8 heat exchangers
9 Reaktor zur Methanolherstellung9 Reactor for the production of methanol
10 Kesselspeisewasser10 boiler feed water
11 Dampf11 steam
12 methanolhaltiges Synthesegas12 synthesis gas containing methanol
13 Kondensator13 capacitor
14 Methanolabscheider14 methanol separator
15 Rohmethanol15 raw methanol
16 verbleibendes Synthesegas16 remaining synthesis gas
17 Kreisgasverdichter17 cycle gas compressors
18 Spülgas 18 purge gas

Claims

Patentansprüche claims
1. Verfahren zur katalytischen Methanolherstellung unter Druck aus Synthesegas, welches mindestens Wasserstoff, Kohlenmonoxid, Kohlendioxid und außerdem unerwünschte Verunreinigungen enthält, mit wenigstens einer Stufe, die einen Reaktor enthält, dadurch gekennzeichnet, dass jedem katalytischen Reaktionssystem zur Hersteilung von Methanol eine Absorptionsstufe vorgeschaltet wird, welche als Absorptionsmittel für die Synthese von Methanol taugliches Katalysatormaterial enthält, und welche Absorptionsstufe bei einer Temperatur betrieben wird, die un- .. terhalb der für die katalytische Umsetzung zu Methanol liegt.1. A process for the catalytic production of methanol under pressure from synthesis gas which contains at least hydrogen, carbon monoxide, carbon dioxide and also undesirable impurities, with at least one stage which contains a reactor, characterized in that an absorption stage is connected upstream of each catalytic reaction system for the production of methanol, which contains catalyst material suitable as an absorbent for the synthesis of methanol, and which absorption stage is operated at a temperature which is below that for the catalytic conversion to methanol.
2. Verfahren nach Anspruch , dadurch gekennzeichnet, dass als Absorptionsmaterial Katalysatormaterial mit der Zusammensetzung 30 bis 50 % CuO, 30 bis 50 % ZnO und 10 bis 30 % AI2O3 eingesetzt wird.2. The method according to claim, characterized in that catalyst material with the composition 30 to 50% CuO, 30 to 50% ZnO and 10 to 30% Al 2 O 3 is used as the absorption material.
3. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass in der Absorptionsvorrichtung eine Absorptionstemperatur zwischen 100 °C und3. The method according to any one of claims 1 to 2, characterized in that in the absorption device an absorption temperature between 100 ° C and
200 °C, vorzugsweise 150 °C bis 160 °C, eingestellt wird.200 ° C, preferably 150 ° C to 160 ° C, is set.
4. Anlage zur Durchführung der katalytischen Methanolherstellung nach Anspruch 1 , dadurch gekennzeichnet, dass die Absorptionsvorrichtung als einfacher zylindrischer Behälter mit Einbauten zum Festhalten der Schüttung, während sie in axialer oder radial Richtung durchströmt wird, ausgeführt wird, ferner mit jeweils stirnseitigen Öffnungen für den Gaseintritt und -austritt, sowie der Möglichkeit, Katalysatormaterial einzufüllen oder zu entnehmen.4. Plant for carrying out the catalytic methanol production according to claim 1, characterized in that the absorption device is designed as a simple cylindrical container with internals for holding the bed while it is being flowed through in the axial or radial direction, furthermore with respective end openings for the gas inlet and outlet, as well as the ability to fill in or remove catalyst material.
5. Anlage nach Anspruch 4 gekennzeichnet durch 2 parallel miteinander verschaltete Behälter, die jeweils einzeln gasseitig absperrbar sind, so dass eine Füllung oder Entleerung von Katalysatormaterial möglich ist, während sich der jeweils andere Behälter bestimmungsgemäß in Betrieb befindet. 5. System according to claim 4, characterized by 2 parallel interconnected containers, each of which can be individually shut off on the gas side, so that a filling or emptying of catalyst material is possible while the other container is in operation as intended.
EP02782960A 2001-11-16 2002-10-19 Method for catalytic production of methanol and a device for implementing said method Withdrawn EP1444185A2 (en)

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