DE4324905A1 - Dehydrogenation catalyst and its use - Google Patents
Dehydrogenation catalyst and its useInfo
- Publication number
- DE4324905A1 DE4324905A1 DE4324905A DE4324905A DE4324905A1 DE 4324905 A1 DE4324905 A1 DE 4324905A1 DE 4324905 A DE4324905 A DE 4324905A DE 4324905 A DE4324905 A DE 4324905A DE 4324905 A1 DE4324905 A1 DE 4324905A1
- Authority
- DE
- Germany
- Prior art keywords
- calculated
- weight
- oxide
- catalyst
- ethylbenzene
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 235000013980 iron oxide Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- UBUHAZKODAUXCP-UHFFFAOYSA-N iron(2+);oxygen(2-);hydrate Chemical class O.[O-2].[Fe+2] UBUHAZKODAUXCP-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical class [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- KZKCOVQRXJUGDG-UHFFFAOYSA-N praseodymium Chemical compound [Pr][Pr] KZKCOVQRXJUGDG-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 229910006540 α-FeOOH Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
Abstract
Description
Die Erfindung betrifft einen Katalysator für die Dehydrierung insbesondere von Ethylbenzol zu Styrol in Gegenwart von Wasser dampf sowie die Verwendung des Katalysators für diesen Zweck.The invention relates to a catalyst for dehydrogenation in particular from ethylbenzene to styrene in the presence of water steam as well as the use of the catalyst for this purpose.
Hierzu sind die nachstehenden Druckschriften in Betracht zu zie hen:For this purpose, the following documents are to be considered hen:
- (1) US-PS 4 144 197(1) U.S. Patent 4,144,197
- (2) DE-PS 28 03 175(2) DE-PS 28 03 175
- (3) DE-PS 28 15 874(3) DE-PS 28 15 874
- (4) EP-PS 195 252(4) EP-PS 195 252
- (5) US-PS 3 223 743.(5) U.S. Patent 3,223,743.
Styrol ist ein wichtiger Ausgangsstoff für die Herstellung von Kunststoffen, synthetischen Harzen und verschiedenen Kautschuken.Styrene is an important raw material for the production of Plastics, synthetic resins and various rubbers.
Styrol wird technisch durch Überleiten von Ethylbenzol zusammen mit Wasserdampf über einen i.a. fest angeordneten Katalysator bei Temperaturen zwischen 500 und 700°C hergestellt. Bei diesem Ver fahren gibt es je nach Art der Wärmezuführung eine isotherme und eine adiabatische Ausführungsform (vgl. 1). Eine ausführliche Be schreibung der Verfahren findet sich im Kunststoff-Handbuch, Bd. V, Polystyrol, Karl-Hanser-Verlag, auf den Seiten 39-47 (1969). Dort sind auch geeignete Katalysatoren beschrieben, die im wesentlichen aus Gemischen verschiedener Metalloxide bestehen. Die technisch wichtigsten Katalysatoren haben Eisenoxid als Hauptbestandteil, dem oxidbildende Alkalisalze sowie struktursta bilisierende, aktivitäts- und selektivitätssteigernde Metall verbindungen zugemischt werden. So werden in (1-3) Katalysatoren mit Vanadinoxid, Wolframoxid, Ceroxid, Chromoxid und Kobaltoxid und in (4) Katalysatoren mit Wolframoxid, Ceroxid und Erdalkali metallen als Promotoren beschrieben.Styrene is technically composed by passing ethylbenzene over it with steam over an i.a. fixed catalyst at Temperatures between 500 and 700 ° C made. In this Ver Depending on the type of heat supply, there is an isothermal and an adiabatic embodiment (see Fig. 1). A detailed Be description of the procedures can be found in the Plastics Handbook, Vol. V, polystyrene, Karl-Hanser-Verlag, on pages 39-47 (1969). There are also described suitable catalysts, the consist essentially of mixtures of different metal oxides. The most technically important catalysts have iron oxide as Main component, the oxide-forming alkali salts and struktursta Bilisierende, activity and selectivity-enhancing metal compounds are mixed. Thus, in (1-3) catalysts with vanadium oxide, tungsten oxide, cerium oxide, chromium oxide and cobalt oxide and in (4) catalysts with tungsten oxide, ceria and alkaline earth metals described as promoters.
In den technischen Verfahren werden große Stoffmengen umgesetzt, so daß selbst eine kleine Verbesserung der Ausbeute von wirt schaftlichem Interesse ist. Die Ausbeute wird zum einen von der Selektivität, zum anderen von der Aktivität des Katalysators be stimmt. Die Ausbeute ist das Produkt aus Selektivität und Umsatz (im allgemeinen in Prozent des rechnerisch möglichen Werts ange geben, wobei sich "Umsatz" auf den Umsatz in einem Verfahrenszug bezieht; natürlich kann der Umsatz durch Auftrennen der Verfahrensprodukte und Rückführung unveränderten Ethylbenzols auf 100% gesteigert werden). Günstig ist demnach ein Katalysator, welcher sowohl eine hohe Selektivität als auch eine hohe Aktivität besitzt. Im allgemeinen sind diese Eigenschaften einan der gegenläufig, d. h. ein selektiver Katalysator ist meist wenig aktiv und umgekehrt. Die Zugabe von selektivitätssteigernden Promotoren führt oft zu einer Verringerung der Aktivität, so daß höhere Rückgewinnungskosten für das nicht umgesetzte Ethylbenzol entstehen. Im Rahmen der Selektivität unterscheidet man bei den gebildeten Nebenprodukten zwischen wieder einsetzbaren Produkten, wie z. B. Benzol, und dem Ergebnis der Totaloxidation, d. h. irre versiblen Verlusten: Nebenprodukte wie Benzol können zur Gewin nung von Ethylbenzol eventuell wieder verwendet werden und so die Ausbeute des Gesamtverfahrens steigern. Günstig ist es also, ins besondere die Totaloxidation, d. h. die CO₂-Bildung, zu minimieren.In the technical process, large amounts of substance are converted, so that even a small improvement in the yield of wirt of economic interest. The yield is on the one hand by the Selectivity, on the other hand by the activity of the catalyst be Right. The yield is the product of selectivity and turnover (generally in percent of the mathematically possible value give, where "sales" on sales in a procedure refers; Of course, sales can be broken by separating the Process products and recycling unchanged ethylbenzene on 100% increase). Favorable is therefore a catalyst, which has both a high selectivity and a high Has activity. In general, these properties are one the opposite, d. H. a selective catalyst is usually little active and vice versa. The addition of selectivity enhancing Promoters often leads to a reduction in activity, so that higher recovery costs for the unreacted ethylbenzene arise. In the context of selectivity one distinguishes among the formed by-products between reusable products, such as Benzene, and the result of total oxidation, d. H. crazy Versatile losses: By-products such as benzene can lead to the gain tion of ethylbenzene may be reused and so on Increase the yield of the overall process. It is favorable, therefore, in the especially the total oxidation, d. H. the CO₂ formation, to minimize.
Die Lebensdauer eines Katalysators ist ebenfalls ein wichtiges Ziel; hierfür ist die Zugabe von strukturstabilisierenden Kompo nenten entscheidend. Diese Strukturstabilisatoren können gleich zeitig Promotoren sein; sie beeinflussen Selektivität und Aktivität. In (5) wird die Kombination Chromoxid/Ceroxid als Strukturstabilisator und Promotor vorgeschlagen.The lifetime of a catalyst is also important Aim; this is the addition of structure-stabilizing Kompo crucial. These structural stabilizers can be the same be promoters at an early stage; they affect selectivity and Activity. In (5), the combination of chromium oxide / ceria is used as Structure stabilizer and promoter proposed.
Zusätzlich wird bei Katalysatoren der ökologische Aspekt aus Gründen der Deponierfähigkeit ein zunehmend wichtiger Faktor bei der Entwicklung von Katalysatoren; im vorliegenden Fall bedeutet das, daß der Katalysator z. B. wenig oder kein Chrom enthalten soll.In addition, the ecological aspect of catalysts becomes apparent Landfill capacity is an increasingly important factor the development of catalysts; in the present case means that the catalyst z. B. contain little or no chromium should.
Ausgehend von diesem Stand der Technik bestand die Aufgabe, einen Katalysator für die Dehydrierung von alkylierten Aromaten, insbe sondere von Ethylbenzol zu Styrol, bei gleichzeitig höherer Aktivität und Selektivität vorzuschlagen, der sich unter den Re aktionsbedingungen selbst regeneriert und eine möglichst geringe Totaloxidation bewirkt. Außerdem sollte er ökologisch verträgli cher sein als die bekannten Katalysatoren.Based on this prior art, the task was a Catalyst for the dehydrogenation of alkylated aromatics, esp special of ethylbenzene to styrene, at the same time higher To propose activity and selectivity, which can be found under the Re conditions of regeneration itself and the lowest possible Total oxidation causes. In addition, he should be ecologically compatible cher than the known catalysts.
Die Lösung dieser Aufgabe gelingt durch einen Katalysator der eingangs genannten Art. Die Erfindung betrifft daher einen Katalysator, der enthält:The solution of this problem is achieved by a catalyst of The invention therefore relates to a catalyst, which contains:
- (a) 40 bis 90 Gew.-% Eisen, berechnet als Fe₂O₃;(A) 40 to 90 wt .-% iron, calculated as Fe₂O₃;
- (b) 5 bis 40 Gew.-% Kalium, berechnet als K₂O;(b) 5 to 40% by weight of potassium, calculated as K₂O;
- (c) 0,01 bis 10 Gew.-% Vanadium, berechnet als V₂O₅; (c) from 0.01% to 10% by weight of vanadium calculated as V₂O₅;
- (d) 0,01 bis 20 Gew.-% Wolfram, berechnet als WO₃;(d) from 0.01% to 20% by weight tungsten calculated as WO₃;
- (e) 0, 01 bis 30 Gew.-% einer Seltenen Erde, berechnet als Oxid der jeweils höchsten Oxidationsstufe;(e) 0, 01 to 30 wt .-% of a rare earth, calculated as oxide the highest oxidation state in each case;
- (f) 0,01 bis 15 Gew.-% Aluminium, berechnet als Al₂O₃;(f) 0.01 to 15% by weight of aluminum, calculated as Al₂O₃;
- (g) bis 10 Gew.-% Kobalt, berechnet als CoO.(g) to 10% by weight of cobalt, calculated as CoO.
Die Bestandteile a) bis f) bzw. g) machen im gebrauchsfertigen Katalysator in der Regel 100% aus. Bei der Herstellung können Verformungshilfsmittel, wie Graphit, Cellulose, Stearate, Stärke, Bentonit, Portlandzement etc. benutzt werden, wobei organische Zusätze bei der Calcinierung des Katalysators i.a. abbrennen und somit die Zusammensetzung des Katalysators nicht wesentlich be einflussen. Die nachstehend genannte Zusammensetzung bezieht sich immer auf die oxidierte Form, also vor der Benutzung und frei von Hilfsmitteln. Es versteht sich, daß die Oxide der beteiligten Elemente auch untereinander Verbindungen eingehen können, die dann u. U. etwa röntgenkristallographisch gefunden werden.The ingredients a) to f) or g) make ready for use Catalyst usually 100% off. In the production can Deformation aids, such as graphite, cellulose, stearates, starch, Bentonite, Portland cement etc. are used, with organic Additives in the calcination of the catalyst i.a. burn down and Thus, the composition of the catalyst is not essential be influences. The composition mentioned below relates always on the oxidized form, so before use and free from Aids. It is understood that the oxides of the involved Elements can also make connections with each other, the then u. U. may be found by X-ray crystallography.
Der erfindungsgemäße Katalysator enthält die vorstehend genannten Elemente z. B. als Oxide; vorzugsweise enthält erThe catalyst according to the invention contains the abovementioned Elements z. As oxides; preferably it contains
- (a) 50 bis 90 Gew.-% eines Eisenoxids, berechnet als Fe₂O₃;(A) 50 to 90 wt .-% of an iron oxide, calculated as Fe₂O₃;
- (b) 9 bis 20 Gew.-% Kaliumoxid, berechnet als stabilstes Oxid (K₂O)(b) 9 to 20% by weight of potassium oxide, calculated as the most stable oxide (K₂O)
- (c) 0,01 bis 8 Gew.-% eines Vanadiumoxids, berechnet als Vana diumpentoxid;(c) 0.01 to 8% by weight of a vanadium oxide calculated as Vana diumpentoxid;
- (d) 0,01 bis 10 Gew.-% eines Wolframoxids, berechnet als Wolfram trioxid;(d) 0.01 to 10% by weight of a tungsten oxide, calculated as tungsten trioxide;
- (e) 0,01 bis 20 Gew.-% eines Oxids der Seltenen Erde, berechnet als Oxid in der jeweils höchsten Oxidationsstufe;(e) 0.01 to 20% by weight of a rare earth oxide calculated as oxide in the highest oxidation state;
- (f) 0,01 bis 10 Gew.-% Aluminiumoxid, berechnet als Oxid;(f) 0.01 to 10% by weight of alumina, calculated as oxide;
- (g) 0 bis 8 Gew.-% Kobaltoxid, berechnet als CoO.(g) 0 to 8% by weight of cobalt oxide calculated as CoO.
Andere Elemente können, je nach Auflösungsvermögen des analyti schen Verfahrens, in mehr oder minder geringen Mengen gefunden werden, insbesondere Elemente, die mit den vorgenannten verge sellschaftet sind und von Dehydrierkatalysatoren her ohnehin be kannt sind. Der erfindungsgemäße Katalysator ist insoweit nicht empfindlich.Other elements may, depending on the resolution of the analyti method, found in more or less small quantities be, in particular elements verge with the aforementioned are gesetenet and dehydrogenation catalysts forth ago be are known. The catalyst of the invention is not so far sensitive.
Als Eisenverbindung können verschiedene Eisenoxide oder Eisen oxidhydrate verwendet werden. Bevorzugt verwendet man fein kristalline, gelbe (α-FeOOH), rote (α-Fe₂O₃) oder schwarze (Fe₃O₄) Pigmente.As an iron compound, various iron oxides or iron oxide hydrates are used. Preference is given to using fine crystalline, yellow (α-FeOOH), red (α-Fe₂O₃) or black (Fe₃O₄) Pigments.
Als Kaliumverbindung sind das Oxid, Hydroxid, Carbonat, Hydrogen carbonat oder Kaliumsalze, welche beim Erhitzen in das Oxid über gehen geeignet. Im allgemeinen wird Kaliumcarbonat bevorzugt.As the potassium compound, the oxide, hydroxide, carbonate, hydrogen carbonate or potassium salts, which on heating in the oxide on go suitable. In general, potassium carbonate is preferred.
Vanadium kann als Vanadiumpentoxid oder in Form von Salzen oder anderer in die Oxide thermisch zerlegbarer Verbindungen wie der Sulfate oder Vanadate zugegeben werden; evt. wird dabei auch z. B. Kalium mit eingebracht.Vanadium can be used as vanadium pentoxide or in the form of salts or Other in the oxides of thermally decomposable compounds such as Sulfates or vanadates are added; evt. It is also z. B. Potassium introduced.
Wolfram wird vorzugsweise in Form von Wolframverbindungen, z. B. des Oxids oder einer Verbindung, welche beim Calcinieren das Oxid ergibt (z. B. Wolframsäure), zugegeben.Tungsten is preferably in the form of tungsten compounds, e.g. B. of the oxide or a compound which upon calcining the oxide gives (eg tungstic acid) added.
Die Seltenen Erden werden ebenfalls als Verbindungen, z. B. als Nitrate, Hydroxide, vorzugsweise aber als Oxide, Carbonate oder Oxalate eingesetzt. Von den Seltenen Erden werden dabei Cer, Pra seodym und Europium bevorzugt.The rare earths are also used as compounds, e.g. B. as Nitrates, hydroxides, but preferably as oxides, carbonates or Oxalates used. Of the rare earths, Cer, Pra seodymium and europium preferred.
Aluminium wird vorzugsweise in Form von Aluminiumoxid oder z. B. als AlOOH zugegeben.Aluminum is preferably in the form of alumina or z. B. added as AlOOH.
Als Kobaltverbindung sind das Oxid, Hydroxid, Carbonat, Hydrogen carbonat oder Kobaltsalze, welche beim Erhitzen das Oxid ergeben geeignet. Im allgemeinen wird Kobaltcarbonat bevorzugt.As cobalt compound are the oxide, hydroxide, carbonate, hydrogen carbonate or cobalt salts, which upon heating give the oxide suitable. In general, cobalt carbonate is preferred.
Der erfindungsgemäße Katalysator kann auf verschiedene Weise er halten werden. Die feingepulverten Bestandteile können in Wasser suspendiert und sprühgetrocknet oder, was einfacher ist, nur trocken gemischt werden.The catalyst of the invention can in various ways he to hold. The finely powdered ingredients can be dissolved in water suspended and spray-dried or, which is easier, only be mixed dry.
Das trockene Pulver wird, evt. nach Zugabe eines geeigneten Ver formungshilfsmittels, entweder mechanisch zu stabilen Formkörpern tablettiert oder unter Zugabe von Wasser zu einer pastösen Masse angezeigt und zu Strängen extrudiert. Die Extrudate werden ge trocknet und können bei 300 bis 1000°C ein- oder zweistufig calci niert werden; evtl. kann man sie auch unmittelbar in die vorgese henen Reaktoren einfüllen und dort einer Endbehandlung unterzie hen, bevor das Verfahren in Betrieb gesetzt wird.The dry powder is, possibly after addition of a suitable Ver forming assistant, either mechanically stable moldings tableted or with the addition of water to a pasty mass displayed and extruded into strands. The extrudates are ge dries and can be calcined at 300 to 1000 ° C in one or two stages be defined; maybe you can also directly in the vorgese fill in the reactors and subject them to a final treatment before the procedure is put into operation.
Die Bestandteile werden ggf. pulverisiert, sorgfältig vermischt und nach Zugabe von 170 Teilen Wasser 3 Stunden geknetet. Die pastöse Masse wird zu Strängen mit einem Durchmesser von 6 mm ex trudiert, eine Stunde bei 80°C getrocknet und anschließend zwei Stunden einer Wärmebehandlung bei 350°C und schließlich 90 Minuten bei 650°C unterworfen. Auch die in Beispielen beschriebenen ande ren Katalysatoren wurden so hergestellt. Zum Vergleich ist das Ergebnis eines Versuchs aufgeführt, bei dem ein Katalysator aus 77,9% Fe₂O₃, 12,6% K₂O, 2,3% Wo₃, 2,7% Ce₂O₃, 1,2% Cr₂O₃ und 0,3% CoO gemäß dem Beispiel in Tabelle IX der DE-PS 28 15 874 verwendet wurde.The ingredients are optionally pulverized, mixed thoroughly and kneaded for 3 hours after adding 170 parts of water. The pasty mass becomes strands with a diameter of 6 mm ex triturated, dried at 80 ° C for one hour and then two Hours of heat treatment at 350 ° C and finally 90 minutes subjected to 650 ° C. Also the ande described in examples ren catalysts were prepared. For comparison, that is Result of an experiment in which a catalyst out 77.9% Fe₂O₃, 12.6% K₂O, 2.3% Wo₃, 2.7% Ce₂O₃, 1.2% Cr₂O₃ and 0.3% CoO according to the example in Table IX of DE-PS 28 15 874 was used.
Von den hergestellten Katalysatoren werden jeweils 550 g in einen Versuchsreaktor mit 30 m Innendurchmesser eingefüllt. Pro Stunde werden 265 g Wasserdampf und 155 g Ethylbenzoldampf mit einer Temperatur von 200°C in den Reaktor dosiert. Die Temperatur des Reaktors wird mit einer Elektroheizung jeweils so eingestellt, daß die organische Phase des Reaktoraustrags 60% Styrol enthält. Nach 10 Tagen wird eine Gesamtanalyse der organischen Phase und des Abgases durchgeführt und die Selektivität des Katalysators errechnet. Of the catalysts produced in each case 550 g in a Pilot reactor filled with 30 m internal diameter. Per hour 265 g of steam and 155 g ethylbenzene vapor with a Temperature of 200 ° C metered into the reactor. The temperature of the Reactor is set with an electric heater each so the organic phase of the reactor discharge contains 60% of styrene. After 10 days, a total analysis of the organic phase and performed the exhaust gas and the selectivity of the catalyst calculated.
Claims (2)
- (a) 40 bis 90 Gew.-% Eisen, berechnet als Fe₂O₃;
- (b) 5 bis 40 Gew.-% Kalium, berechnet als K₂O;
- (c) 0,01 bis 10 Gew.-% Vanadium, berechnet als V₂O₅;
- (d) 0,01 bis 20 Gew.-% Wolfram, berechnet als WO₃;
- (e) 0,01 bis 30 Gew.-% einer Seltenen Erde, berechnet als Oxid der jeweils höchsten Oxidationsstufe;
- (f) 0,01 bis 15 Gew.-% Aluminium, berechnet als Al₂O₃;
- (g) bis 10 Gew.-% Kobalt, berechnet als CoO.
- (A) 40 to 90 wt .-% iron, calculated as Fe₂O₃;
- (b) 5 to 40% by weight of potassium, calculated as K₂O;
- (c) from 0.01% to 10% by weight of vanadium calculated as V₂O₅;
- (d) from 0.01% to 20% by weight tungsten calculated as WO₃;
- (e) 0.01 to 30% by weight of a rare earth calculated as the oxide of the highest oxidation state;
- (f) 0.01 to 15% by weight of aluminum, calculated as Al₂O₃;
- (g) to 10% by weight of cobalt, calculated as CoO.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4324905A DE4324905A1 (en) | 1993-07-24 | 1993-07-24 | Dehydrogenation catalyst and its use |
| NL9401143A NL9401143A (en) | 1993-07-24 | 1994-07-11 | Dehydrogenation catalyst and its use. |
| IT94MI001470A ITMI941470A1 (en) | 1993-07-24 | 1994-07-14 | DEHYDROGENATION CATALYST AND ITS USE |
| FR9409051A FR2707892B3 (en) | 1993-07-24 | 1994-07-21 | Dehydrogenation catalyst and its use for the dehydrogenation of ethylbenzene. |
| GB9414781A GB2280126A (en) | 1993-07-24 | 1994-07-22 | Dehydrogenation catalyst and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4324905A DE4324905A1 (en) | 1993-07-24 | 1993-07-24 | Dehydrogenation catalyst and its use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4324905A1 true DE4324905A1 (en) | 1995-01-26 |
Family
ID=6493635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE4324905A Withdrawn DE4324905A1 (en) | 1993-07-24 | 1993-07-24 | Dehydrogenation catalyst and its use |
Country Status (5)
| Country | Link |
|---|---|
| DE (1) | DE4324905A1 (en) |
| FR (1) | FR2707892B3 (en) |
| GB (1) | GB2280126A (en) |
| IT (1) | ITMI941470A1 (en) |
| NL (1) | NL9401143A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1342710A2 (en) * | 2002-03-04 | 2003-09-10 | Korea Research Institute Of Chemical Technology | Method for catalytic dehydrogenation of hydrocarbons using carbon dioxide as a soft oxidant |
| CN106582693A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low temperature alkyl arene dehydrogenation catalyst and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19814081A1 (en) * | 1998-03-30 | 1999-10-07 | Basf Ag | Catalyst for the dehydrogenation of 1,1-diphenylethane and substituted 1,1-diarylethanes |
| CN100430133C (en) * | 2005-12-14 | 2008-11-05 | 中国石油化工股份有限公司 | Low-water ratio ethylbenzene dehydrogenation catalyst |
| US20100081855A1 (en) * | 2008-09-30 | 2010-04-01 | Fina Technology, Inc. | Semi-Supported Dehydrogenation Catalyst |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1108114A (en) * | 1977-04-14 | 1981-09-01 | Gregor H. Riesser | Dehydrogenation catalyst |
| IN148558B (en) * | 1977-04-14 | 1981-04-04 | Shell Int Research | |
| DE3132014A1 (en) * | 1981-08-13 | 1983-03-03 | Basf Ag, 6700 Ludwigshafen | DEHYDRATION CATALYST, METHOD FOR PRODUCING THE SAME AND USE FOR DEHYDRATING ETHYLBENZENE TO STYRENE |
| EP0112754B1 (en) * | 1982-12-14 | 1986-11-05 | Institut Français du Pétrole | Catalyst containing oxides of iron, chrominium, potassium and lanthanum, its preparation and its use in dehydrogenation reactions |
| DE3521766A1 (en) * | 1985-06-19 | 1987-01-02 | Basf Ag | HONEYCOMB CATALYST, ITS PRODUCTION AND USE |
| US4758543A (en) * | 1987-07-01 | 1988-07-19 | The Dow Chemical Company | Dehydrogenation catalyst |
-
1993
- 1993-07-24 DE DE4324905A patent/DE4324905A1/en not_active Withdrawn
-
1994
- 1994-07-11 NL NL9401143A patent/NL9401143A/en not_active Application Discontinuation
- 1994-07-14 IT IT94MI001470A patent/ITMI941470A1/en not_active IP Right Cessation
- 1994-07-21 FR FR9409051A patent/FR2707892B3/en not_active Expired - Fee Related
- 1994-07-22 GB GB9414781A patent/GB2280126A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1342710A2 (en) * | 2002-03-04 | 2003-09-10 | Korea Research Institute Of Chemical Technology | Method for catalytic dehydrogenation of hydrocarbons using carbon dioxide as a soft oxidant |
| EP1342710A3 (en) * | 2002-03-04 | 2004-01-21 | Korea Research Institute Of Chemical Technology | Method for catalytic dehydrogenation of hydrocarbons using carbon dioxide as a soft oxidant |
| CN106582693A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low temperature alkyl arene dehydrogenation catalyst and preparation method thereof |
| CN106582693B (en) * | 2015-10-16 | 2019-11-08 | 中国石油化工股份有限公司 | Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2280126A (en) | 1995-01-25 |
| FR2707892A3 (en) | 1995-01-27 |
| NL9401143A (en) | 1995-02-16 |
| ITMI941470A0 (en) | 1994-07-14 |
| GB9414781D0 (en) | 1994-09-14 |
| FR2707892B3 (en) | 1995-06-02 |
| ITMI941470A1 (en) | 1995-01-24 |
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