NL9401143A - Dehydrogenation catalyst and its use. - Google Patents
Dehydrogenation catalyst and its use. Download PDFInfo
- Publication number
- NL9401143A NL9401143A NL9401143A NL9401143A NL9401143A NL 9401143 A NL9401143 A NL 9401143A NL 9401143 A NL9401143 A NL 9401143A NL 9401143 A NL9401143 A NL 9401143A NL 9401143 A NL9401143 A NL 9401143A
- Authority
- NL
- Netherlands
- Prior art keywords
- calculated
- oxide
- catalyst
- weight
- ethylbenzene
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 33
- 238000006356 dehydrogenation reaction Methods 0.000 title claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910018404 Al2 O3 Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-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
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 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
- 239000004793 Polystyrene Substances 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
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 230000002708 enhancing effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 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
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 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
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
Description
Dehvdrogeneringskatalvsator en de toepassing daarvanDehydrogenation catalyst and its application
De uitvinding heeft betrekking op een katalysator voor de dehydroge-nering van in het bijzonder ethylbenzeen tot styreen bij aanwezigheid van waterdamp, alsmede de toepassing van de katalysator voor dit doel.The invention relates to a catalyst for the dehydrogenation of, in particular, ethylbenzene to styrene in the presence of water vapor, and the use of the catalyst for this purpose.
Hiertoe moeten de volgende publicaties in beschouwing worden genomen: (1) US-A-4.144.197 (2) DE-C-2.803.175 (3) DE-C-2.8l5.874 (4) EP-B-195.252 (5) US-A-3.223.743.To this end, the following publications should be considered: (1) US-A-4,144,197 (2) DE-C-2,803,175 (3) DE-C-2.8l5.874 (4) EP-B-195.252 ( 5) US-A-3,223,743.
Styreen is een belangrijke grondstof voor de bereiding van kunststoffen, synthetische harsen en verschillende soorten rubber.Styrene is an important raw material for the preparation of plastics, synthetic resins and various types of rubber.
Styreen wordt technisch bereid door ethylbenzeen samen met waterdamp over een in het algemeen vast aangebrachte katalysator bij temperaturen tussen 500 en 700°C te leiden. Bij deze werkwijze bestaat, afhankelijk van het type warmtetoevoer, een isotherme en een adibatische uitvoeringsvorm (zie 1). Een uitgebreide beschrijving van de werkwijzen staat in het Kunststoff-Handbuch, deel V, Polystyreen, Karl-Hanser-Verlag, op de bladzijden 39-47 (1969). Daar worden ook geschikte katalysatoren beschreven, die in hoofdzaak uit mengsels van verschillende metaaloxiden bestaan. De technisch belangrijkste katalysatoren bevatten ijzeroxide als de belangrijkste component, waaraan oxide vormende alkalimetaalzouten, alsmede de struktuur stabiliserende, de activiteit en selectiviteit verhogende metaalverbindingen worden toegemengd. Aldus worden in (1-3) katalysatoren met vanadiumoxide, wolfraamoxide, ceriumoxide, chroomoxide en kobaltoxide en in (4) katalysatoren met wolfraamoxide, ceriumoxide en aardalkalimetalen als promoters beschreven.Styrene is technically prepared by passing ethylbenzene along with water vapor over a generally fixed catalyst at temperatures between 500 and 700 ° C. Depending on the type of heat supply, this method consists of an isothermal and an adibatic embodiment (see 1). A detailed description of the methods can be found in the Kunststoff-Handbuch, part V, Polystyrene, Karl-Hanser-Verlag, on pages 39-47 (1969). Suitable catalysts are also described there, consisting essentially of mixtures of different metal oxides. The technically most important catalysts contain iron oxide as the main component, to which oxide-forming alkali metal salts, as well as metal stabilizing, activity and selectivity enhancing metal compounds, are added. Thus, in (1-3) catalysts with vanadium oxide, tungsten oxide, cerium oxide, chromium oxide and cobalt oxide and in (4) catalysts with tungsten oxide, cerium oxide and alkaline earth metals are described as promoters.
Bij de technische werkwijzen worden grote hoeveelheden materiaal omgezet, zodat zelfs een kleine verbetering van de opbrengst van economisch belang is. De opbrengst wordt enerzijds door de selectiviteit en anderzijds door de activiteit van de katalysator bepaald. De opbrengst is het produkt van de selectiviteit en de omzetting (in het algemeen als percentage van de rekenkundig mogelijke waarde aangegeven, waarbij "omzetting" betrekking heeft op de omzetting in een stap; natuurlijk kan de omzetting door het scheiden van de reaktieprodukten en het terugvoeren van ethylbenzeen, dat niet heeft gereageerd, tot 100# worden vergroot). Derhalve is een katalysator gunstig, die zowel een hoge selectiviteit alsook een grote activiteit bezit. In het algemeen zijn deze eigenschappen met elkaar in strijd, d.w.z. dat een selectieve katalysator vaak weinig actief is en omgekeerd. Het toevoegen van promoters die de de selectiviteit vergroten leidt vaak tot een afname van de activiteit, zodat hogere kosten voor het terugwinnen van ethylbenzeen dat niet is omgezet ontstaan. In het kader van de selectiviteit maakt men bij de gevormde nevenprodukten onderscheid tussen opnieuw te gebruiken produk-ten, zoals b.v. benzeen, en het resultaat van de volledige oxidatie, d.w.z. irreversibele verliezen: nevenprodukten zoals benzeen kunnen eventueel opnieuw worden gebruikt voor het winnen van ethylbenzeen en aldus de opbrengst van de totale werkwijze vergroten. Derhalve is het dus gunstig om in het bijzonder de totale oxidatie, d.w.z. de vorming van C02, te minimaliseren.In the technical processes, large amounts of material are converted, so that even a small improvement in yield is of economic importance. The yield is determined on the one hand by the selectivity and on the other by the activity of the catalyst. The yield is the product of the selectivity and the conversion (generally indicated as a percentage of the arithmetically possible value, where "conversion" refers to the conversion in one step; of course, the conversion can be effected by separating the reaction products and recycling of unreacted ethylbenzene to be increased to 100 #). Therefore, a catalyst is advantageous, which has both high selectivity and high activity. In general, these properties conflict with each other, i.e. a selective catalyst is often inactive and vice versa. The addition of promoters that increase selectivity often leads to a decrease in activity, resulting in higher recovery costs of unreacted ethylbenzene. In the context of selectivity, a distinction is made in the by-products formed between reusable products, such as e.g. benzene, and the result of complete oxidation, i.e. irreversible losses: by-products such as benzene can optionally be reused to recover ethylbenzene and thus increase the yield of the overall process. It is therefore advantageous to minimize in particular the total oxidation, i.e. the formation of CO2.
De levensduur van een katalysator is eveneens een belangrijk doel; hiervoor is het toevoegen van componenten die de struktuur stabiliseren van belang. Deze struktuurstabilisatoren kunnen tegelijkertijd promoters zijn; ze beïnvloeden de selectiviteit en de activiteit. In (5) wordt de combinatie chroomoxide/ceriumoxide als struktuurstabilisator en promoter voorgesteld.The life of a catalyst is also an important goal; for this it is important to add components that stabilize the structure. These structure stabilizers can simultaneously be promoters; they affect selectivity and activity. In (5), the chromium oxide / cerium oxide combination is proposed as a structure stabilizer and promoter.
Daarnaast wordt bij katalysatoren het ecologische aspect vanwege redenen van de afvalverwerking een steeds belangrijkere faktor bij de ontwikkeling van katalysatoren; in het onderhavige geval betekent dit, dat de katalysator b.v. weinig of geen chroom mag bevatten.In addition, the ecological aspect of catalysts is becoming an increasingly important factor in the development of catalysts for reasons of waste processing; in the present case this means that the catalyst e.g. may contain little or no chromium.
Uitgaande van deze stand der techniek was het doel, een katalysator voor de dehydrogenering van gealkyleerde aromaten, in het bijzonder van ethylbenzeen tot styreen, bij een tegelijkertijd grotere activiteit en selectiviteit te verschaffen, die zich onder de reaktieomstandigheden zelf regenereert en een zo klein mogelijke totale oxidatie veroorzaakt. Bovendien moet deze ecologisch beter verdraagbaar zijn dan de bekende katalysatoren.Starting from this prior art, the object was to provide a catalyst for the dehydrogenation of alkylated aromatics, especially from ethylbenzene to styrene, at the same time providing greater activity and selectivity, which regenerates itself under the reaction conditions and minimizes overall oxidation. Moreover, it must be ecologically more tolerable than the known catalysts.
Het bereiken van dit doel wordt tot stand gebracht door een katalysator van het soort dat in de aanhef is genoemd. De uitvinding heeft derhalve betrekking op een katalysator die bevat: (a) 40 tot 90 gew.% ijzer, berekend als Fe203; (b) 5 tot 40 gew.% kalium, berekend als K20; (c) 0,01 tot 10 gew.% vanadium, berekend als V205; (d) 0,01 tot 20 gew.% wolfraam, berekend als W03; (e) 0,01 tot 30 gew.% van een zeldzame aarde, berekend als oxide met steeds de hoogste oxidatietrap; (f) 0,01 tot 15 gew.# aluminium, berekend als A1203; (g) tot 10 gew.# kobalt, berekend als CoO.The attainment of this goal is accomplished by a catalyst of the type mentioned in the preamble. The invention therefore relates to a catalyst containing: (a) 40 to 90% by weight of iron, calculated as Fe 2 O 3; (b) 5 to 40% by weight of potassium, calculated as K 2 O; (c) 0.01 to 10 wt% vanadium, calculated as V 2 O 5; (d) 0.01 to 20 wt% tungsten, calculated as WO3; (e) 0.01 to 30% by weight of a rare earth, calculated as oxide with the highest oxidation stage in each case; (f) 0.01 to 15 wt% aluminum, calculated as Al2 O3; (g) up to 10% by weight of cobalt, calculated as CoO.
De componenten a) tot en met f) resp. g) vormen in de gebruiksgerede katalysator in de regel 100#. Bij de bereiding kunnen vervormingshulpmid-delen, zoals grafiet, cellulose, stearaten, zetmeel, bentoniet, Portland-cement enz., worden gebruikt, waarbij organische toevoegsels in het algemeen bij de calcinering van de katalysator afbranden, en dus de samenstelling van de katalysator, niet wezenlijk beïnvloeden. De hierna genoemde samenstelling heeft steeds betrekking op de geoxideerde vorm, dus voor gebruik en vrij van hulpmiddelen. Het spreekt vanzelf dat de oxiden van de deelnemende elementen ook met elkaar verbindingen kunnen vormen, die dan eventueel door röntgenkristallografie kunnen worden gevonden.Components a) to f) resp. g) usually form 100 # in the ready-to-use catalyst. In the preparation, deformation aids such as graphite, cellulose, stearates, starch, bentonite, Portland cement, etc. can be used, with organic additives generally burning off during the calcination of the catalyst, and thus the catalyst composition, not materially affect. The composition mentioned below always refers to the oxidized form, i.e. for use and free from auxiliaries. It goes without saying that the oxides of the participating elements can also form connections with each other, which can then possibly be found by X-ray crystallography.
De katalysator volgens de uitvinding bevat de hiervoor genoemde elementen b.v. als oxiden; bij voorkeur bevat deze (a) 50 tot 90 gew.# van een ijzeroxide, berekend als Fe203; (b) 9 tot 20 gew.% kaliumoxide, berekend als gestabiliseerd oxide (K20); (c) 0,01 tot 8 gew.% van een vanadiumoxide, berekend als vanadium-pentoxide; (d) 0,01 tot 10 gew.% van een wolfraamoxide, berekend als wolfraam-trioxide; (e) 0,01 tot 20 gew.# van een oxide van de zeldzame aarden, berekend als oxide met steeds de hoogste oxidatietrap; (f) 0,01 tot 10 gew.% aluminiumoxide, berekend als oxide; (g) 0 tot 8 gew.% kobaltoxide, berekend als CoO.The catalyst according to the invention contains the aforementioned elements, e.g. as oxides; preferably it contains (a) 50 to 90% by weight of an iron oxide, calculated as Fe 2 O 3; (b) 9 to 20% by weight of potassium oxide, calculated as stabilized oxide (K20); (c) 0.01 to 8% by weight of a vanadium oxide, calculated as vanadium pentoxide; (d) 0.01 to 10% by weight of a tungsten oxide, calculated as tungsten trioxide; (e) 0.01 to 20% by weight of an oxide of the rare earths, calculated as oxide with the highest oxidation stage in each case; (f) 0.01 to 10% by weight aluminum oxide, calculated as oxide; (g) 0 to 8% by weight of cobalt oxide, calculated as CoO.
Andere elementen kunnen, afhankelijk van het oplossend vermogen van de analytische werkwijze, in grotere of kleinere hoeveelheden worden gevonden, in het bijzonder elementen die samen met de hiervoor genoemde voorkomen en die met betrekking tot dehydrogeneringskatalysatoren toch al bekend zijn. De katalysator volgens de uitvinding is voor zover niet gevoelig.Other elements, depending on the resolving power of the analytical process, can be found in larger or smaller amounts, in particular elements which occur together with the aforementioned and which are already known with regard to dehydrogenation catalysts. The catalyst according to the invention is insensitive as far as it is concerned.
Als ijzerverbinding kunnen verscheidene ijzeroxiden of ijzeroxide-hydraten worden gebruikt. Bij voorkeur gebruikt men fijnkristallijne gele (α-FeOOH), rode (a-Fe203) of zwarte (Fe30i,) pigmenten.Various iron oxides or iron oxide hydrates can be used as the iron compound. Preferably, crystalline yellow (α-FeOOH), red (α-Fe 2 O 3) or black (Fe 3 O 1) pigments are used.
Als kaliumverbinding zijn het oxide, hydroxide, carbonaat, water-stofcarbonaat of de kaliumzouten, die bij verhitten overgaan in het oxide, geschikt. In het algemeen heeft kaliumcarbonaat de voorkeur.As the potassium compound, the oxide, hydroxide, carbonate, hydrogen carbonate or the potassium salts which transition to the oxide when heated are suitable. Generally, potassium carbonate is preferred.
Vanadium kan als vanadiumpentoxide of in de vorm van zouten of andere, thermisch in de oxiden te ontleden verbindingen, zoals de sulfaten of vanadaten, worden toegevoegd; eventueel wordt daarmee ook b.v. kalium toegevoegd.Vanadium can be added as vanadium pentoxide or in the form of salts or other compounds to be decomposed thermally in the oxides, such as the sulfates or vanadates; optionally, e.g. potassium added.
Wolfraam wordt bij voorkeur in de vorm van wolfraamverbindingen, b.v. het oxide of een verbinding die bij het calcineren het oxide geeft (b.v. wolfraamzuur), toegevoegd.Tungsten is preferably in the form of tungsten compounds, e.g. the oxide or a compound which gives the oxide during calcination (e.g. tungsten acid).
De zeldzame aarden worden eveneens als verbindingen, b.v. als nitraten, hydroxiden, bij voorkeur echter als oxiden, carbonaten of oxalaten, toegevoegd. Van de zeldzame aarden hebben daarbij cerium, praseodymium en europium de voorkeur.The rare earths are also used as compounds, e.g. as nitrates, hydroxides, but preferably as oxides, carbonates or oxalates. Of the rare earths, cerium, praseodymium and europium are preferred.
Aluminium wordt bij voorkeur in de vorm van aluminiumoxide of b.v. als A100H toegevoegd.Aluminum is preferably in the form of alumina or e.g. added as A100H.
Als kobaltverbinding zijn het oxide, hydroxide, carbonaat, waterstof carbonaat of de kobaltzouten, die bij verhitten het oxide geven, geschikt. In het algemeen heeft kobaltcarbonaat de voorkeur.As the cobalt compound, the oxide, hydroxide, carbonate, hydrogen carbonate or the cobalt salts which give the oxide when heated are suitable. Cobalt carbonate is generally preferred.
De katalysator volgens de uitvinding kan op verschillende wijzen worden verkregen. De componenten met een fijne poedervorm kunnen in water worden gesuspendeerd en gesproeidroogd of, hetgeen eenvoudiger is, alleen droog worden gemengd.The catalyst of the invention can be obtained in various ways. The fine powdered components can be suspended in water and spray dried or, which is simpler, mixed dry only.
Het droge poeder wordt, eventueel na toevoegen van een geschikt vervormingshulpmiddel, ofwel mechanisch tot stabiele voorwerpen getablet-teerd of onder toevoeging van water tot een pasteuze massa verwerkt en tot strengen geëxtrudeerd. De extrudaten worden gedroogd en kunnen bij 300 tot 1000°C in een of twee trappen worden gecalcineerd; eventueel kan men ze ook onmiddellijk aan de beoogde reaktoren toevoegen en daar aan een laatste behandeling onderwerpen voordat de werkwijze wordt aangevangen.The dry powder, optionally after addition of a suitable deformation aid, is either mechanically tableted into stable objects or processed into a pasty mass with the addition of water and extruded into strands. The extrudates are dried and can be calcined in one or two stages at 300 to 1000 ° C; if desired, they can also be added immediately to the intended reactors and subjected to a final treatment there before the process is started.
De componenten worden eventueel verpulverd, zorgvuldig gemengd en na het toevoegen van 170 delen water 3 uur gekneed. De pasteuze massa wordt tot strengen met een diameter van 6 mm geëxtrudeerd, een uur bij 80°C gedroogd en vervolgens twee uur aan een warmtebehandeling bij 350°C en tenslotte 90 minuten aan een warmtebehandeling bij 650°C onderworpen. Ook de in de voorbeelden beschreven andere katalysatoren worden aldus bereid. Ter vergelijking wordt het resultaat van een test gegeven, waarbij een katalysator van 77,9% Fe203, 12,6* K20, 2,3# W03, 2,7% Ce203, 1,2% Cr203 en 0,3% CoO volgens het voorbeeld in tabel IX van DE-C-2.8l5.874 werd gebruikt.If necessary, the components are pulverized, carefully mixed and kneaded for 3 hours after adding 170 parts of water. The pasty mass is extruded into strands with a diameter of 6 mm, dried at 80 ° C for one hour and then heat-treated at 350 ° C for two hours and finally heat-treated at 650 ° C for 90 minutes. The other catalysts described in the examples are also prepared in this way. For comparison, the result of a test is given, in which a catalyst of 77.9% Fe2O3, 12.6 * K20, 2.3 # WO3, 2.7% Ce203, 1.2% Cr203 and 0.3% CoO according to the example in Table IX of DE-C-2.815.874 was used.
Van de bereide katalysatoren wordt steeds 550 g in een testreaktor met een inwendige diameter van 30 mm gevuld. Per uur worden 265 g waterdamp en 155 g ethylbenzeendamp met een temperatuur van 200eC in de reak-tor gedoseerd. De temperatuur van de reaktor wordt door middel van een elektrische verwarming steeds zodanig ingesteld, dat de organische fase van het uitgangsprodukt van de reaktor 60% styreen bevat. Na 10 dagen wordt een totaalanalyse van de organische fase en het afvalgas uitgevoerd en de selectiviteit van de katalysator berekend.550 g of the prepared catalysts are charged in a test reactor with an internal diameter of 30 mm. 265 g of water vapor and 155 g of ethylbenzene vapor at a temperature of 200 ° C are metered into the reactor per hour. The temperature of the reactor is always adjusted by means of an electric heater so that the organic phase of the reactor's starting product contains 60% styrene. After 10 days, a total analysis of the organic phase and the waste gas is carried out and the selectivity of the catalyst is calculated.
Claims (2)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4324905A DE4324905A1 (en) | 1993-07-24 | 1993-07-24 | Dehydrogenation catalyst and its use |
DE4324905 | 1993-07-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
NL9401143A true NL9401143A (en) | 1995-02-16 |
Family
ID=6493635
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NL9401143A NL9401143A (en) | 1993-07-24 | 1994-07-11 | 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) |
Families Citing this family (5)
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 |
KR20030072541A (en) * | 2002-03-04 | 2003-09-15 | 한국화학연구원 | Novel Method for Catalytic Dehydrogenation of Hydrocarbons Using Carbon Dioxide as Soft Oxidant |
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 |
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 |
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 |
DE3367335D1 (en) * | 1982-12-14 | 1986-12-11 | Inst Francais Du Petrole | 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
Also Published As
Publication number | Publication date |
---|---|
FR2707892A3 (en) | 1995-01-27 |
GB9414781D0 (en) | 1994-09-14 |
FR2707892B3 (en) | 1995-06-02 |
DE4324905A1 (en) | 1995-01-26 |
ITMI941470A1 (en) | 1995-01-24 |
ITMI941470A0 (en) | 1994-07-14 |
GB2280126A (en) | 1995-01-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4144197A (en) | Dehydrogenation catalyst | |
CA1108114A (en) | Dehydrogenation catalyst | |
EP0112017B1 (en) | Catalysts for para-ethyltoluene dehydrogenation | |
RU2038146C1 (en) | Catalyst for oxidation ammonolysis of propylene | |
US2414585A (en) | Catalytic dehydrogenation | |
MXPA01008496A (en) | Compositions comprising nickel and their use as catalyst in oxidative dehydrogenation of alkanes. | |
US6130183A (en) | Catalyst for oxidative dehydrogenation of paraffinic hydrocarbons and use of this catalyst | |
US7186395B2 (en) | Iron oxides with a higher degree of refining | |
NL9401143A (en) | Dehydrogenation catalyst and its use. | |
CA1099695A (en) | Chromium-free catalyst | |
EP1025069A1 (en) | USE OF Ce/Zr MIXED OXIDE PHASE FOR THE MANUFACTURE OF STYRENE BY DEHYDROGENATION OF ETHYLBENZENE | |
US3821324A (en) | Oxidative dehydrogenation processes | |
US3887631A (en) | Oxidative dehydrogenation of hydrocarbons | |
US3907916A (en) | Dehydrogenation of alkyl aromatic hydrocarbons | |
RU2218986C2 (en) | Catalytic system and method of oxidative dehydrogenation of alkylaromatic hydrocarbons or paraffins up to corresponding alkynyl-aromatic hydrocarbons or up to corresponding olefins | |
US4000176A (en) | Process for simultaneously producing methacrylo-nitrile and butadiene by vapor-phase catalytic oxidation of mixed butenes | |
US3928389A (en) | Oxidative dehydrogenation of alkenes or alkadienes to furan compounds | |
EP0282314B1 (en) | Method for ammoxidation of paraffins and catalyst therefor | |
EP0093518A1 (en) | Catalysts for para-ethyltoluene dehydrogenation | |
EP0030837A1 (en) | Dehydrocoupling of toluene | |
JPH069443A (en) | Production of monoalkenylbenzene | |
US2217011A (en) | Process of converting acetylenic hydrocarbons to aromatic hydrocarbons | |
US4484017A (en) | Olefin aromatization process | |
US2436616A (en) | Dehydrogenation process | |
US2958717A (en) | Catalytic dehydrogenation of hydrocarbons |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
BV | The patent application has lapsed |