DE102005004926A1 - New catalyst system having catalyst activity increases in flow direction of gas, for catalytic gaseous phase reactions and for preparing e.g. phthalic acid, where the catalyst activity is steered by mixing low/high active catalysts - Google Patents
New catalyst system having catalyst activity increases in flow direction of gas, for catalytic gaseous phase reactions and for preparing e.g. phthalic acid, where the catalyst activity is steered by mixing low/high active catalysts Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 230000000694 effects Effects 0.000 title claims abstract description 33
- 239000007789 gas Substances 0.000 title claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 6
- 238000002156 mixing Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 title abstract description 5
- 239000007792 gaseous phase Substances 0.000 title abstract 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 title 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005977 Ethylene Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001273 butane Substances 0.000 claims abstract description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008096 xylene Substances 0.000 claims abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000010574 gas phase reaction Methods 0.000 claims description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003570 air Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003716 rejuvenation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- 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
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/003—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor in a downward flow
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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Abstract
Description
Die vorliegende Erfindung betrifft Katalysatorsysteme für katalytische Gasphasenreaktionen, die dadurch gekennzeichnet sind, dass die Katalysatoraktivität in Flussrichtung des Gases zunimmt, wobei die Katalysatoraktivität durch Mischungen aus niedrig aktiven und hoch aktiven Katalysatoren gesteuert wird. Ferner betrifft die Erfindung Verfahren zur Herstellung von Phthalsäureanhydrid, Ethylendichlorid, Cyclohexanon, Acrylsäure und Maleinsäureanhydrid, wobei die Edukte in dem genannten Katalysatorsystem umgesetzt werden.The The present invention relates to catalyst systems for catalytic Gas phase reactions, characterized in that the catalyst activity in the flow direction of the gas increases, wherein the catalyst activity by mixtures of low active and highly active catalysts is controlled. Further concerns the invention process for the preparation of phthalic anhydride, Ethylene dichloride, cyclohexanone, acrylic acid and maleic anhydride, wherein the reactants are reacted in said catalyst system.
Bekanntermaßen wird eine Vielzahl von katalytischen Gasphasenreaktionen in einem Festbettreaktor durchgeführt. Dazu wird beispielsweise ein Gemisch aus einem molekularen Sauerstoff enthaltenden Gas und das zu oxidierende Ausgangsmaterial durch eine Vielzahl in einem Reaktor angeordneter Rohren geleitet, in denen sich eine Schüttung mindestens eines Katalysators befindet. Zur Temperaturregelung sind die Rohre von einem Wärmeträgermedium, beispielsweise einer Salzschmelze umgeben. Trotz dieser Thermostatisierung kann es in der Katalysatorschüttung zur Ausbildung sogenannter „hot spots" kommen, in denen eine höhere Temperatur herrscht als im übrigen Teil der Katalysatorschüttung. Diese hot spots geben Anlass zu Nebenreaktionen, wie beispielsweise der Totalverbrennung des Ausgangsmaterials oder führen zur Bildung schwer abtrennbarer Nebenprodukte. Ferner beschleunigen die hot spots die Alterung der Katalysatoren.As is known a variety of catalytic gas phase reactions in a fixed bed reactor carried out. For this example, a mixture of a molecular oxygen containing gas and the starting material to be oxidized by a Variety passed in a reactor arranged pipes, in which at least one batch a catalyst is located. For temperature control are the pipes from a heat transfer medium, For example, surrounded by a molten salt. Despite this thermostatting It can be in the catalyst bed for training so-called "hot spots "come in which one higher Temperature prevails as in the rest Part of the catalyst bed. These hot spots give rise to side reactions, such as the total combustion of the starting material or lead to Formation of difficult to separate by-products. Further accelerate the hot spots the aging of the catalysts.
Zur Abschwächung dieser hot spots wurde in der Technik dazu übergegangen, unterschiedlich aktive Katalysatoren schichtweise in der Katalysatorschüttung anzuordnen, wobei sich in der Regel der weniger aktive Katalysator zum Gaseintritt hin befindet und folglich das Reaktionsgemisch zuerst mit ihm in Kontakt kommt, wohingegen sich der aktivere Katalysator zum Gasaustritt aus der Katalysatorschüttung hin befindet.to attenuation This hot spot has been changed in technology, different to arrange active catalysts layer by layer in the catalyst bed, which is usually the less active catalyst for gas entry and therefore the reaction mixture first with him in Contact comes, whereas the more active catalyst to the gas outlet from the catalyst bed is located.
Die Art und Weise der Aktivitätsstrukturierung ist vielfältig. Nach dem unter anderem in der EP-A 1 063 222 auf dem Gebiet der Herstellung von Phthalsäureanhydrid zusammengefassten Stand der Technik kann die Aktivitätssteigerung auf sehr verschiedenen Wegen erfolgen:
- (1) durch stetigen Anstieg des Phosphor-, Vanadiumpentoxid- oder Antimonoxidge halts,
- (2) durch stetigen Anstieg des Aktivmassengehalts,
- (3) durch stetige Abnahme des Alkaligehalts,
- (4) durch stetige Abnahme des Leerraumes zwischen den einzelnen Katalysatoren,
- (5) durch stetige Abnahme des Gehalts an Inertstoffen,
- (6) durch stetige Zunahme der Temperatur oder
- (7) durch stetige Zunahme der Titandioxid-Oberfläche
- (1) by steadily increasing the phosphorus, vanadium pentoxide or antimony oxide content,
- (2) by a steady increase in the active mass content,
- (3) by steady decrease of the alkali content,
- (4) by a steady decrease in the void space between the individual catalysts,
- (5) by steadily decreasing the content of inert materials,
- (6) by steady increase in temperature or
- (7) by continuous increase of titanium dioxide surface
Aktivitätsstrukturierte Katalysatorschüttungen werden nicht nur bei der Herstellung von Carbonsäuren oder Carbonsäureanhydriden eingesetzt, sondern beispielsweise auch bei der Gasphasenoxychlorierung von Ethylen zu Ethylendichlorid oder bei der Dehydrierung von Cyclohexanol zu Cyclohexanon (K. Weissermel, H.-J. Arpe, Industrielle Organische Chemie, VCH Verlag Weinheim).Structured activity catalyst beds not only in the production of carboxylic acids or carboxylic anhydrides used, but for example in the Gasphasenoxychlorierung from ethylene to ethylene dichloride or in the dehydrogenation of cyclohexanol to cyclohexanone (K. Weissermel, H.-J. Arpe, Industrielle Organische Chemistry, VCH Verlag Weinheim).
Die Anzahl der Aktivitätsstufen ist durch den Aufwand der Katalysatorpräparation und des Katalysatorbefüllens limitiert. Trotz eines mehrlagigen Katalysatorsystems können sich immer noch ausgeprägte hot spots ausbilden, die sich negativ auf die Ausbeute auswirken und die Alterung des Katalysators beschleunigen.The Number of activity levels is limited by the expense of catalyst preparation and catalyst filling. Despite a multi-layer catalyst system can still pronounced hot train spots that have a negative impact on the yield and accelerate the aging of the catalyst.
Um ein mehrlagiges Katalysatorsystem zu befüllen, wurde in der Technik dazu übergegangen, das manuelle Befüllen, in dem über ein Trichter in jedes einzelne Rohr eine abgemessene Menge Katalysatormaterial eingefüllt wurde, durch automatisches Befüllen zu ersetzen. Eine automatische Befüllung von Rohren mit Katalysatoren ist beispielsweise aus der US-A 4 402 643 bekannt. Dieses Dokument beschreibt ein auf Rollen verfahrbares Rahmengestell mit sich in Granulataustragungsrichtung verjüngenden Behältern. Aus diesem gelangt das Schüttgut in einen mittels einer Vibrationseinheit rüttelbaren Trog, der in nebeneinander liegenden Längsrinnen unterteilt ist. An der Seite des Trogs sind Anschlusselemente vorgesehen, an denen flexible Schläuche befestigt sind, über welche das Schüttgut den Rohrbündelreaktoren zugeführt werden kann.Around To fill a multilayer catalyst system has been known in the art passed to that manual filling, in the over a funnel into each individual tube a measured amount of catalyst material filled was, by automatic filling to replace. An automatic filling of pipes with catalysts is known for example from US-A 4,402,643. This document describes a movable on wheels frame with in Rejuvenating Granulataustragungsrichtung Containers. From this the bulk material arrives in a vibratable by means of a vibration unit trough, in side by side lying longitudinal channels is divided. On the side of the trough connection elements are provided, where flexible hoses are attached, over which the bulk material the tube bundle reactors supplied can be.
Die Aufgabe bestand demnach darin, ein Katalysatorsystem aufzufinden, dessen Aktivität in Flussrichtung des Katalysators zunimmt, ohne dass eine Vielzahl von verschiedenen Katalysatortypen eingesetzt werden muss. Insbesondere bestand die Aufgabe darin, ein vereinfachtes aktivitätsstrukturiertes Katalysatorsystem aufzuzeigen, dass eine kontinuierliche Aktivitätssteigerung aufweist. Ferner bestand die Aufgabe darin, Katalysatorsysteme aufzuzeigen, die im Vergleich zum Stand der Technik längere Lebenszeiten aufweisen. Darüber hinaus bestand die Aufgabe darin, Verfahren zur Herstellung von Phthalsäureanhydrid, Ethylendichlorid, Cyclohexanon, Maleinsäureanhydrid und Acrylsäure aufzuzeigen, die eine höhere Ausbeute im Vergleich zum Stand der Technik aufweisen.The object was therefore to find a catalyst system whose activity increases in the direction of flow of the catalyst, without a variety of different types of catalysts must be used. In particular, the object was to show a simplified activity-structured catalyst system that has a continuous increase in activity. Furthermore, the task was to aufzu catalyst systems show that have longer lifetimes compared to the prior art. In addition, the object was to provide processes for the preparation of phthalic anhydride, ethylene dichloride, cyclohexanone, maleic anhydride and acrylic acid, which have a higher yield compared to the prior art.
Es wurde überraschender Weise gefunden, dass sich ein Katalysatorsystem dessen Katalysatoraktivität in Flussrichtung des Gases zunimmt, wobei die Katalysatoraktivität durch Mischungen aus niedrig aktiven und hoch aktiven Katalysatoren gesteuert wird, vorteilhaft für exotherme und endotherme Gasphasenreaktion einsetzen lässt.It became more surprising Manner found that a catalyst system whose catalyst activity in the flow direction of the gas increases, wherein the catalyst activity by mixtures of low active and highly active catalysts is controlled, advantageous for exothermic and use endothermic gas phase reaction.
Zur Steuerung der Katalysatoraktivität werden vorteilhaft weniger als vier verschiedene Katalysatoren eingesetzt. Besonders bevorzugt werden zur Steuerung der Aktivität zwei verschiedenen Katalysatoren eingesetzt, wobei der eine davon (Katalysator A) eine niedrige Aktivität und der andere (Katalysator B) eine hohe Aktivität aufweist.to Control of catalyst activity Advantageously, less than four different catalysts are used. Especially preferred are two different ones for controlling the activity Catalysts used, wherein one of them (Catalyst A) a low activity and the other (Catalyst B) has high activity.
Vorteilhaft ist der Katalysator A hoch-selektiv. Der Katalysator B ist vorteilhaft hoch-aktiv und gegebenenfalls weniger selektiv.Advantageous the catalyst A is highly selective. The catalyst B is advantageous highly active and if necessary less selective.
Vorteilhaft wird die Aktivität der Katalysatoren A und B so eingestellt, dass am Gaseintritt der Katalysatorschüttung hauptsächlich der Katalysator A und am Gasaustritt hauptsächlich der Katalysator B vorliegt.Advantageous becomes the activity the catalysts A and B adjusted so that the gas inlet of the catalyst bed mainly the Catalyst A and at the gas outlet mainly the catalyst B is present.
Die unterschiedliche Aktivität der Katalysatoren A und B kann nach allen den Fachmann bekannten Maßnahmen erfolgen. Beispielsweise kann unterschiedliche Aktivität durch einen unterschiedlichen Aktivmassengehalt, durch eine unterschiedliche Komponentenzusammensetzung in der Aktivmasse, durch einen unterschiedlichen Gehalt an Inertstoffen oder durch eine unterschiedliche Oberfläche einer Katalysatorkomponente erhalten werden.The different activity Catalysts A and B can be known to all those skilled in the art activities respectively. For example, different activity may be due a different active mass content, by a different component composition in the active composition, by a different content of inert substances or through a different surface of a catalyst component to be obtained.
Gegebenenfalls kann am Gaseintritt vor der Stelle der geringsten Katalysatoraktivität eine Zone höherer Aktivität angeordnet sein, um das Anspringen der Reaktion zu herleichtern.Possibly For example, a zone of higher activity may be placed at the gas inlet before the point of lowest catalyst activity be to facilitate the onset of the reaction.
Die Aktivitätssteigerung in der Katalysatorschüttung erfolgt vorteilhaft kontinuierlich. Folglich ist das erfindungsgemäße Katalysatorensystem nicht mehr in einzelne Zonen unterschiedlicher Aktivität aufgeteilt, sondern weist einen kontinuierlichen Übergang von Bereichen geringerer Aktivität zu Bereichen höherer Aktivität auf.The increase in activity in the catalyst bed advantageously takes place continuously. Consequently, the catalyst system according to the invention no longer divided into individual zones of different activity, but has a continuous transition from areas of lesser activity to areas of higher activity on.
Diese kontinuierliche Aktivitätssteigerung ist durch einen kontinuierlichen Anstieg des Mischungsverhältnisses von Katalysator A:B von 1:0 bis 0:1 zu erreichen. Die genauen Mischungsverhältnisse sind an die jeweilige Reaktion und den dazugehörigen Temperaturverlauf anzupassen. Diese Optimierung kann vom Fachmann ohne weiteren Aufwand beispielsweise anhand der Temperaturprofile, Nebenproduktspektren oder der Totalverbrennungs-CO-CO2-Analyse durchgeführt werden.This continuous increase in activity is achieved by a continuous increase in the mixing ratio of catalyst A: B from 1: 0 to 0: 1. The exact mixing ratios must be adapted to the respective reaction and the associated temperature profile. This optimization can be carried out by a person skilled in the art without any further effort, for example on the basis of the temperature profiles, by-product spectra or the total combustion CO-CO 2 analysis.
Das erfindungsgemäße Katalysatorsystem befindet sich vorteilhaft in einem Festbettreaktor, insbesondere in einem Rohrbündelreaktor. Rohrbündelreaktoren sind bei der Durchführung von Gasphasenreaktionen bekannt. Typische Rohrbündelreaktoren weisen bis zu 40 000 einzelne Rohre auf, wobei die einzelnen Rohre in der Regel einen Durchmesser von 1 bis 10 cm aufweisen.The Inventive catalyst system is located advantageous in a fixed bed reactor, in particular in a Tube reactor. Tube reactors are performing known by gas phase reactions. Typical tube bundle reactors exhibit up to 40 000 individual pipes on, with the individual pipes usually have a diameter of 1 to 10 cm.
Die Befüllen der Rohre kann vorteilhaft so erfolgen, dass aus zwei Vorratsbehältern (i) beinhaltend Katalysator A und (ii) beinhaltend Katalysator B kontinuierlich Katalysatoren in einen Mischungsbehälter fließen. Die Art und Weise, in welchem Mischungsverhältnis die Katalysatoren A und B gemischt werden, d. h. in welcher Geschwindigkeit/Menge die Katalysatoren A und B dem Mischungsbehälter zugeführt werden, wird in Abhängigkeit von der Füllhöhe gesteuert. Wird beispielsweise die Gaseintrittsseite befüllt, wird hauptsächlich der Katalysator A dem Mischungsbehälter zugeführt. Im mittleren Bereich der Katalysatorschüttungen liegen die Katalysatoren ungefähr im selben Verhältnis vor, d.h. der Mischungsbehälter wird typischerweise mit gleichen Teilen Katalysator A und B gefüllt. Wird hingegen die Gasaustrittsseite befüllt, wird hauptsächlich der Katalysator B dem Mischungsbehälter zugeführt. Der Mischungsbehälter ist vorteilhaft kein Vorratsbehälter, sondern aus ihm gelangen die Katalysatoren direkt, wie beispielsweise in der US-A 4,402,643 oder in der deutschen Anmeldung mit dem Anmelde-Aktenzeichen 102004012754.9 beschrieben, über eine Förderrinne mit Ablauftrichter in die Rohre.The fill The tubes can advantageously be made so that from two storage containers (i) including catalyst A and (ii) containing catalyst B continuously Catalysts flow into a mixing tank. The way in what mixing ratio the catalysts A and B are mixed, d. H. in which speed / quantity the catalysts A and B are supplied to the mixing tank, is dependent controlled by the filling level. For example, if the gas inlet side filled, is mainly the Catalyst A to the mixing tank fed. in the middle area of the catalyst beds are the catalysts approximately in the same proportion, i.e. the mix tank is typically filled with equal parts of catalyst A and B. Will, however filled the gas outlet side, becomes main the catalyst B fed to the mixing tank. The mix tank is advantageously no storage container, but from him get the catalysts directly, such as in US-A 4,402,643 or in the German application with the application file number 102004012754.9 described above a conveyor trough with drainage funnel into the pipes.
Besonders vorteilhaft ist das erfindungsgemäße Katalysatorsystem für exotherme Gasphasenreaktionen, insbesondere zur Herstellung von Phthalsäureanhydrid, Ethylendichlorid, Acrylsäure, Maleinsäureanhydrid oder Cyclohexanon.Especially Advantageously, the catalyst system according to the invention for exothermic Gas-phase reactions, in particular for the production of phthalic anhydride, Ethylene dichloride, acrylic acid, maleic anhydride or cyclohexanone.
Allerdings lässt sich das erfindungsgemäße Katalysatorsystem auch für endotherme Reaktionen vorteilhaft einsetzen.Indeed let yourself the catalyst system according to the invention also for use endothermic reactions advantageous.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung von Phthalsäureanhydrid durch Gasphasenoxidation von Xylol, Naphthalin oder Gemischen davon, wobei Xylol, Naphthalin oder Gemische davon und ein molekularen Sauerstoff enthaltendes Gas in dem erfindungsgemäßen Katalysatorsystem umgesetzt werden.The The invention further relates to a process for the preparation of phthalic anhydride by gas phase oxidation of xylene, naphthalene or mixtures thereof, wherein xylene, naphthalene or mixtures thereof and a molecular Oxygen-containing gas implemented in the catalyst system of the invention become.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung von Ethylendichlorid durch Gasphasen-Oxychlorierung von Ethylen, wobei Ethylen mit Salzsäure und Luft oder Sauerstoff zu Ethylendichlorid in dem erfindungsgemäßen Katalysatorsystem umgesetzt werden.The The invention further relates to a process for the production of ethylene dichloride by gas phase oxychlorination of ethylene, wherein ethylene with hydrochloric acid and Air or oxygen reacted to ethylene dichloride in the catalyst system of the invention become.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung von Cyclohexanon durch Gasphasen-Dehydrierung von Cyclohexanol, wobei Cyclohexanol zu Cyclohexanon und Wasserstoff in dem erfindungsgemäßen Katalysatorsystem umgesetzt wird.The The invention further relates to a process for the preparation of cyclohexanone by gas-phase dehydrogenation of cyclohexanol, with cyclohexanol to cyclohexanone and hydrogen in the catalyst system of the invention is implemented.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung von Maleinsäureanhydrid durch Benzol-, Butan- oder Butenoxidation, wobei Benzol, Butan oder Buten und Luft bzw. Sauerstoff zu Maleinsäureanhydrid in dem erfindungsgemäßen Katalysatorsystem umgesetzt werden.The The invention further relates to a process for the preparation of maleic anhydride by benzene, butane or butene oxidation, benzene, butane or Butene and air or oxygen to maleic anhydride in the catalyst system of the invention be implemented.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung von Acrylsäure durch Gasphasenoxidation von Propen und Dampf oder Luft zu Acrolein in einem ersten Katalysatorsystem und die Weiteroxidation von Acrolein in einem zweiten Katalysatorsystem zu Acrylsäure, wobei das erste oder das zweite oder beide Katalysatorsysteme erfindungsgemäß ausgelegt sind. Gegebenenfalls kann einer der zwei Reaktoren nach dem Stand der Technik ausgestattet sein.The The invention further relates to a process for the preparation of acrylic acid Gas phase oxidation of propene and steam or air to acrolein in a first catalyst system and the further oxidation of acrolein in a second catalyst system to acrylic acid, wherein the first or the second or both catalyst systems designed according to the invention are. Optionally, one of the two reactors may be up to date be equipped with the technology.
Durch den Einsatz des erfindungsgemäßen Katalysatorsystems können die hohen Kosten, die durch die Präparation vieler verschiedener Katalysatoren und durch das aufwendige Befüllen der einzelnen Katalysatorlagen anfallen, eingespart werden.By the use of the catalyst system according to the invention can the high costs caused by preparation of many different Catalysts and by the complicated filling of the individual catalyst layers to be saved.
Claims (9)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005004926A DE102005004926A1 (en) | 2005-02-02 | 2005-02-02 | New catalyst system having catalyst activity increases in flow direction of gas, for catalytic gaseous phase reactions and for preparing e.g. phthalic acid, where the catalyst activity is steered by mixing low/high active catalysts |
| PCT/EP2006/050616 WO2006082215A2 (en) | 2005-02-02 | 2006-02-02 | Catalyst system for catalytic gas phase reactions featuring an increasing catalyst activity in the direction of flow of the gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005004926A DE102005004926A1 (en) | 2005-02-02 | 2005-02-02 | New catalyst system having catalyst activity increases in flow direction of gas, for catalytic gaseous phase reactions and for preparing e.g. phthalic acid, where the catalyst activity is steered by mixing low/high active catalysts |
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| DE102005004926A1 true DE102005004926A1 (en) | 2006-08-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7462727B2 (en) | 2003-07-25 | 2008-12-09 | Basf Aktiengesellschaft | Multimetal oxide containing silver, vanadium and a promoter metal and use thereof |
| DE102020129303A1 (en) | 2020-11-06 | 2022-05-12 | Linde Gmbh | Process and plant for the production of one or more hydrocarbons |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007116018A1 (en) * | 2006-04-12 | 2007-10-18 | Basf Se | Catalyst system for preparing carboxylic acids and/or carboxylic anhydrides |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0099431B1 (en) * | 1982-07-20 | 1987-10-28 | Amoco Corporation | Process for production of maleic anhydride |
-
2005
- 2005-02-02 DE DE102005004926A patent/DE102005004926A1/en not_active Withdrawn
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2006
- 2006-02-02 WO PCT/EP2006/050616 patent/WO2006082215A2/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7462727B2 (en) | 2003-07-25 | 2008-12-09 | Basf Aktiengesellschaft | Multimetal oxide containing silver, vanadium and a promoter metal and use thereof |
| DE102020129303A1 (en) | 2020-11-06 | 2022-05-12 | Linde Gmbh | Process and plant for the production of one or more hydrocarbons |
| WO2022096592A1 (en) | 2020-11-06 | 2022-05-12 | Linde Gmbh | Process and plant for producing one or more hydrocarbons |
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| Publication number | Publication date |
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| WO2006082215A3 (en) | 2006-12-28 |
| WO2006082215A2 (en) | 2006-08-10 |
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