GB2280126A - Dehydrogenation catalyst and its use - Google Patents
Dehydrogenation catalyst and its use Download PDFInfo
- Publication number
- GB2280126A GB2280126A GB9414781A GB9414781A GB2280126A GB 2280126 A GB2280126 A GB 2280126A GB 9414781 A GB9414781 A GB 9414781A GB 9414781 A GB9414781 A GB 9414781A GB 2280126 A GB2280126 A GB 2280126A
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- United Kingdom
- Prior art keywords
- weight
- calculated
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims description 37
- 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 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 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 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-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
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 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
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 235000013980 iron oxide Nutrition 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000465 moulding Methods 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
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
- HJVIUZHNRJYUTG-UHFFFAOYSA-N Dehydrocrenation Natural products N1C2=CC=CC=C2C2=C1C(C=C)=NC=C2OC HJVIUZHNRJYUTG-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide 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
- 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
- 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
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 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
- 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
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 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
- 150000003112 potassium compounds Chemical class 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
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 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
- 238000005979 thermal decomposition reaction Methods 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
- 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
- 238000002424 x-ray crystallography Methods 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
is 2280126 Dehydrocrenation catalvat and its use The present invention
relates to a catalyst for the dehydrogenation of, in particular, ethylbenzene to styrene in the presence of steam, and to the use of the catalyst for this purpose.
The relevant literature includes the following:
(1) U.S. Patent 4,144,197 (2) German Patent 2,803,175 (3) German Patent 2,815,874 (4) European Patent 195,252 (5) U.S. Patent 3,223,743.
Styrene is an important starting material for the preparation of plastics, synthetic resins and various rubbers.
Styrene is produced industrially by passing ethylbenzene together with steam over a generally fixedbed catalyst at from 500 to 7000C. This process has an isothermal and an adiabatic form, depending on the method of heat supply' (cf. 1). A detailed description of the processes appears in Kunstotoff-Handbuch, Vol. V, Polystyrol, Karl -Hans er-Verlag, pages 39-47 (1969). Suitable catalysts, which essentially consist of mixtures of various metal oxides are also described here. The catalysts which are most important industrially contain iron oxide as a main component, with which oxide-fo=ing alkali metal salts and structure- stabilizing, activityand selectivity-enhancing metal compounds are mixed. Thus, (1-3) describe catalysts containing vanadium oxide, tungsten oxide, cerium oxide, chromium oxide and cobalt oxide, and (4) describes catalysts containing tungsten oxide, cerium oxide and alkaline earth metals as promoters.
In the industrial processes, large amounts of substances are reacted, so that even a small improvement in the yield is of economic interest. The yield is determined on the one hand by the selectivity and on the other hand by the activity of the catalyst. The yield is 0.Z. 0050/44183 the product of selectivity and conversion (in general stated as a percentage of the theoretical value, conversion relating to the conversion in one operation; of course, the conversion can be increased 100% by separating the products of the process and recycling unchanged ethylbenzene). Accordingly, a catalyst which has both a high selectivity and a high activity is advantageous. In general, these properties are contradictory, ie. a selective catalyst generally has little activity and vice versa. The addition of selectivity-enhancing promoters often leads to a reduction in the activity, so that higher recovery costs for the unconverted ethylbenzene are incurred. In connection with the selectivity, a distinction is made, in the case of the byproducts formed, between reusable products, eg. benzene, and the result of the total oxidation, ie. irreversible losses: byproducts such as benzene may be reused for obtaining ethylbenzene and thus increase the yield of the total process. It is therefore advantageous to minimize in particular the total oxidation, ie. the formation of C02 The lif e of a catalyst is also an important object; the addition of structure-stabilizing components is decisive for this purpose. These structure stabilizers may simultaneously be promoters; they influence the selectivity and activity. (5) proposes the combination chromium oxide/cerium oxide as structure stabilizer and promoter.
Furthermore, in the case of catalysts, the ecological aspect is becoming an increasingly important f actor in the development of catalysts, for reasons of disposability in landfills; in the present case, this means that the catalyst should contain, for example, little or no chromium.
Starting from this prior art, it is an object of the present invention to provide a catalyst for the dehydrogenation of alkylated aromatics, in particular of ethylbenzene to styrene, with higher activity and selec-
1 tivity simultaneously, which catalyst is self-regenerating under the reaction conditions and causes very little total oxidation. Moreover, it should be more ecologically compatible than the known catalysts.
We have found that good results can be achieved by a catalyst which contains (a) from 40 to 90% by weight of iron, calculated as Fe 2 0 3 " (b) from 5 to 40% by weight of potassium, calculated as K 2 0, (c) from 0.01 to 10% by weight of vanadium, calculated as V 2051 (d) from 0.01 to 20% by weight of tungsten, calculated as WO 31 (e) from 0.01 to 30% by weight of a rare earth metal, is calculated as the oxide of the highest oxidation stage in each case, (f) from 0.01 to 15% by weight of aluminum, calculated as (g) Al 2 0 3, and up to 10% by weight of cobalt, calculated as Coo.
Components a) to f) or g) account, as a rule, for 100% in the ready-touse catalyst. Molding assistants, such as graphite, cellulose, stearates, starch, bentonite, Portland cement, etc., may be used in the preparation, organic additives generally being burned off in the calcination of the catalyst and therefore having no substantial effect on the composition of the catalyst. The composition stated below is based in every case on the oxidized form, ie. prior to use and free of assistants. The oxides of the elements involved can of course also form compounds with one another, which may then be detected, for example, by X-ray crystallography.
The novel catalyst contains the above-mentioned elements, for example as oxides; it preferably contains (a) from 50 to 90% by weight of an iron oxide, calculated as Fe 2 0 3 " (d) 0.Z. 0050/44183 (b) from 9 to 20% by weight of potassium oxide, calculated as the most stable oxide M20), f rom 0. 01 to 8% by weight of a vanadium oxide, calculated as vanadium pentoxide, from 0.01 to 10% by weight of a tungsten oxide, calculated as tungsten trioxide, from 0.01 to 20% by weight of an oxide of a rare earth metal, calculated as the oxide in the highest oxidation stage in each case, M from 0.01 to 10% by weight of alumina, calculated as oxide and (g) from 0 to 8% by weight of cobalt oxide, calculated as CoO.
Depending on the resolving power of the analytical method, other elements may be found in greater or smaller amounts, in particular elements which are associated with the abovementioned ones and are in any case known to be used in dehydrogenation catalysts. To this extent, the novel catalyst is not sensitive.
Various iron oxides or hydrated iron oxides can be used as iron compounds. Finely crystalline, yellow ((x-FeOOH), red (a_re2od or black (Fe3o.) pigments are preferably used.
Suitable potassium compounds are the oxide, hydroxide, carbonate, bicarbonate or potassium salts which are converted into the oxide on heating. Potassium carbonate is generally preferred.
Vanadium may be added as vanadium pentoxide or in the form of salts or other compounds capable of thermal decomposition to give the oxides, such as the sulfates or vanadates; for example, potassium may be concomitantly introduced.
Tungsten is preferably added in the form of tungsten compounds, for example in the form of the oxide or of a compound which gives the oxide on calcination (for example tungstic acid).
The rare earth metals are likewise used as i is 0.Z. 0050/44183 compounds, f or example as nitrates or hydroxides, but preferably as oxides, carbonates or oxalates. Preferred rare earth metals are cerium, praseodynium and europium.
Aluminum is pref erably used in the f orm of alumina or, for example, as A100H.
Suitable cobalt compounds are the oxide, hydroxide, carbonate, bicarbonate or cobalt salts which give the oxide on heating. Cobalt carbonate is generally preferred.
The novel catalyst may be obtained by various methods. The finely powdered components are suspended in water and spray-dried or, in a simpler procedure, are only dry-blended.
Possibly af ter the addition of a suitable molding assistant, the dry powder is either pelletized mechanically to give stable moldings or is converted into a pasty material with the addition of water and extruded. The extrudates are dried and can be calcined at from 300 to 100011C inaone-stage or two-stage procedure. They may also be introduced directly into the intended reactors and subjected to a final treatment there before the process is started.
Example
The following is provided (in parts by weight) a-Fe203 1,000 X2C03 300 V205 30 Ce,, (C03) 3 75 A100K CC) (OH) 2 10 The components are, if necessary, powdered and carefully mixed, 170 parts of water are added and the mixture is then kneaded for 3 hours. The pasty material 6 - is 0.Z. 0050/44183 is extruded to give extrudates having a diameter of 6 mm, and the latter are dried for one hour at 80C and then subjected to a heat treatment at 3500C for two hours and finally at 650"C for 90 minutes. The other catalysts described in the Examples were also prepared in this manner. The result of an experiment in which a catalyst comprising 77.9% of Fe2031 12.6% of K20, 2.3% of W03, 2.7% of Ce203, 1.2% of Cr203 and 0.3% of CoO, according to the Example in Table IX of German Patent 2,815,874, was used is given for comparison.
550 g of each of the catalysts prepared are introduced into a test reactor having an internal diameter of 30 mm. 265 g of steam and 155 g of ethylbenzene vapor at 2000C are metered per hour into the reactor. The temperature of the reactor is adjusted by means of an electric heater so that the organic phase of the reacted mixture contains 60% of styrene. After 10 days, a total analysis of organic phase and of the waste gas is carried out and the selectivity of the catalyst is calculated.
1 is 0.Z. 0050/44183 According to the invention Parts by weight Comparative catalyst Parts by weight a-Fe203 1,000 1,000 K2C03 240 240 V205 16 16 Ce2 (C03) 3 55 55 A100H 17 - Cr03 - 17 Co (OH) 2 5 5 Result Selectivity 95.4% 94.9% Reactor temperature 614C 62311C CO. content of waste gas 4.0% 5.4%.
Amount of waste gas 24.0 l(S.T.P.)/h 24.9 l(S.T.P.)/h
Claims (6)
1. A catalyst, in particular for the dehydrogenation of ethylbenzene to styrene in the presence of steam, containing (a) from 40 to 90% by weight of iron, calculated as Fe 203 (b) from 5 to 40% by weight of potassium, calculated as K 2 0, (c) from 0.01 to 10% by weight of vanadium, calculated as v 2 OS# (d) from 0.01 to 20% by weight of tungstenj calculated as WO 3 f (e) from 0.01 to 30% by weight of a rare earth metal, calculated as the oxide of the highest oxidation stage in each case, (f) from 0.01 to 15% by weight of aluminum, calculated as Al 2 0 3, and (g) up to 10% by weight of cobalt, calculated as Coo.
2. A catalyst as claimed in claim 1 comprising from 50 to 90% by weight of an iron oxide, calculated as Fe 2 0 31 and from 9 to 20% by weight of potassium oxide, calculated as K 2 0.
3. A catalyst as claimed in claim 1 or 2 comprising from 0.01 to 8% by weight of a vanadium oxide, calculated as V2051 from 0.01 to 10% by weight of a tungsten oxide, calculated as Wo 31 from 0.01 to 20% by weight of one or more rare earth metal oxides, calculated as the oxide of the highest oxidation state in each case, from 0.01 to 10% by weight of alumina, calculated as Al 2 0 3, and from 0 to 8% by weight of cobalt oxide, calculated as Coo. 30
4. A catalyst as claimed in claim 1 and substantially as hereinbefore exemplified.
5. Use of a catalyst as claimed in any of claims 1 to 4 for the dehydrogenation of ethylbenzene to styrene in the presence of steam.
6. Styrene when produced by dehydrogenation of ethylbenzene in the presence of steam and a catalyst as claimed in any of claims 1 to 4.
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 (2)
| Publication Number | Publication Date |
|---|---|
| GB9414781D0 GB9414781D0 (en) | 1994-09-14 |
| GB2280126A true GB2280126A (en) | 1995-01-25 |
Family
ID=6493635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9414781A Withdrawn GB2280126A (en) | 1993-07-24 | 1994-07-22 | 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999049967A1 (en) * | 1998-03-30 | 1999-10-07 | Basf Aktiengesellschaft | Catalyst for dehydrogenating 1,1-diphenylethanes 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 |
| EP2361237A1 (en) * | 2008-09-30 | 2011-08-31 | Fina Technology, Inc. | Semi-supported dehydrogenation catalyst |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030072541A (en) * | 2002-03-04 | 2003-09-15 | 한국화학연구원 | Novel Method for Catalytic Dehydrogenation of Hydrocarbons Using Carbon Dioxide as Soft Oxidant |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1557142A (en) * | 1977-04-14 | 1979-12-05 | Shell Int Research | Dehydrogenation catalyst |
| GB1557143A (en) * | 1977-04-14 | 1979-12-05 | Shell Int Research | Dehydrogenation catalyst |
| EP0072439A2 (en) * | 1981-08-13 | 1983-02-23 | BASF Aktiengesellschaft | Dehydrogenation catalyst, process for its preparation and its use in the dehydrogenation of ethyl benzene to styrene |
| EP0112240A1 (en) * | 1982-12-14 | 1984-06-27 | Institut Français du Pétrole | Preparation process for a catalyst comprising oxides of iron, chromium, potassium and a rare earth metal, useful in dehydrogenation reactions |
| EP0206193A1 (en) * | 1985-06-19 | 1986-12-30 | BASF Aktiengesellschaft | Honeycomb catalyst, its preparation and use |
| EP0297685A1 (en) * | 1987-07-01 | 1989-01-04 | 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
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1557142A (en) * | 1977-04-14 | 1979-12-05 | Shell Int Research | Dehydrogenation catalyst |
| GB1557143A (en) * | 1977-04-14 | 1979-12-05 | Shell Int Research | Dehydrogenation catalyst |
| EP0072439A2 (en) * | 1981-08-13 | 1983-02-23 | BASF Aktiengesellschaft | Dehydrogenation catalyst, process for its preparation and its use in the dehydrogenation of ethyl benzene to styrene |
| EP0112240A1 (en) * | 1982-12-14 | 1984-06-27 | Institut Français du Pétrole | Preparation process for a catalyst comprising oxides of iron, chromium, potassium and a rare earth metal, useful in dehydrogenation reactions |
| EP0206193A1 (en) * | 1985-06-19 | 1986-12-30 | BASF Aktiengesellschaft | Honeycomb catalyst, its preparation and use |
| EP0297685A1 (en) * | 1987-07-01 | 1989-01-04 | The Dow Chemical Company | Dehydrogenation catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999049967A1 (en) * | 1998-03-30 | 1999-10-07 | Basf Aktiengesellschaft | Catalyst for dehydrogenating 1,1-diphenylethanes 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 |
| EP2361237A1 (en) * | 2008-09-30 | 2011-08-31 | Fina Technology, Inc. | Semi-supported dehydrogenation catalyst |
| EP2361237A4 (en) * | 2008-09-30 | 2013-01-09 | Fina Technology | Semi-supported dehydrogenation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2707892A3 (en) | 1995-01-27 |
| NL9401143A (en) | 1995-02-16 |
| DE4324905A1 (en) | 1995-01-26 |
| ITMI941470A0 (en) | 1994-07-14 |
| ITMI941470A1 (en) | 1995-01-24 |
| FR2707892B3 (en) | 1995-06-02 |
| GB9414781D0 (en) | 1994-09-14 |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |