Patent Application
20180169628
The present invention relates to a catalyst for the dehydrogenation of hydrocarbons which is based on iron oxide and additionally comprises at least one potassium compound, at least one cerium compound, from 0.7 to 10% by weight of at least one manganese compound, calculated as MnO2, and from 10 to 200 ppm of at least one titanium compound, calculated as TiO2, and also to a process for the production thereof. Furthermore, the present invention relates to a process for the catalytic dehydrogenation of hydrocarbons using the catalyst of the invention.
The use of iron oxide-based dehydrogenation catalysts in the dehydrogenation of various hydrocarbons to the corresponding unsaturated hydrocarbons has long been known in the prior art. For example, the dehydrogenation of ethylbenzene to styrene, isopropylbenzene to alpha-methylstyrene, butene to butadiene or isoamylene to isoprene are of industrial importance. The preparation of styrene by heterogeneously catalyzed dehydrogenation of ethylbenzene in the presence of steam is a process which has been carried out industrially since the beginning of the 1930s and has become established as a synthetic route to styrene. Styrene is one of the most important monomers of the plastics industry and is used, for example, for preparing polystyrene, acrylonitrile-butadiene-styrene polymer (ABS) and synthetic rubber.
The iron oxide-based dehydrogenation catalysts described in the prior art are generally multicomponent systems and comprise essentially iron oxide and an alkali metal compound which is, for example, used as alkali metal oxide, carbonate or hydroxide in the production of the catalyst. In addition, these catalysts generally comprise various further active components (promoters), for example oxides of the elements of transition groups 5 and 6 of the Periodic Table or of the rare earths.
The catalytic dehydrogenation of aliphatic or alkylaromatic hydrocarbons is usually carried out industrially in the presence of steam at temperatures in the range from 500 to 700° C. In these processes, the hydrocarbon and the steam are mixed and passed over the iron oxide dehydrogenation catalyst at elevated temperatures.
During the course of the dehydrogenation process, the active sites of the dehydrogenation catalyst typically become blocked as a result of the formation of carbonaceous material during the catalytic dehydrogenation (for example of ethylbenzene to styrene) and gradual deactivation of the catalyst occurs. To reduce this deactivation, steam is added to the hydrocarbon. The steam enables the carbonaceous material formed on the catalyst surface to be gasified in-situ, thus enabling the active catalyst surface to be regenerated. In addition, the steam typically has the following additional functions: supplying the heat of reaction required for the endothermic dehydrogenation reaction, shifting the equilibrium to the product side by reducing the partial pressures of the starting materials, maintaining the oxidation state of the iron notwithstanding the reducing action of hydrogen and hydrocarbon.
The stability and activity of the catalyst are generally higher, the higher the ratio of steam to hydrocarbon (S/HC ratio). However, from the point of view of energy consumption and the operating costs associated therewith, it is desirable to reduce the steam/hydrocarbon ratio. However, a low steam/hydrocarbon ratio typically increases carbonization and irreversible reduction of the dehydrogenation catalyst, so that the catalyst activity decreases after a relatively short time. In addition, a certain amount of steam is normally necessary to supply the required energy to the reaction system.
To ensure satisfactory operating periods of the dehydrogenation process at a low steam/hydrocarbon ratio, the catalysts have to meet particular requirements. In the catalytic dehydrogenation of hydrocarbons, a molar steam/hydrocarbon ratio of less than or equal to 7.35 is generally referred to as a low S/HC ratio. In the case of the dehydrogenation of ethylbenzene, this corresponds approximately to a weight ratio of steam/hydrocarbon of less than or equal to 1.25.
Numerous dehydrogenation catalysts based on iron oxide have been described in the prior art. EP-A 0 181 999 describes dehydrogenation catalysts comprising iron oxide, potassium oxide, magnesium oxide and optionally further metal compounds. The optional addition of from 0 to 10% by weight of a compound Me2O3 where Me=Cr or Mn is described, inter alia. Document EP-A 0 181 999 does not disclose any examples of a dehydrogenation catalyst comprising a manganese compound. In addition, the addition of titanium is not described. The catalyst described in EP-A 0 181 999 is said to have, in particular, an improved stability to boiling water.
The document WO 96/18457 describes a restructured iron oxide having specific particle properties and its use in dehydrogenation catalysts. The restructured iron oxide is said to be obtained by reacting an iron oxide with a restructuring agent, with the restructuring agent being able to be selected, in particular, from among compounds of molybdenum, copper, calcium, zinc, cobalt and cerium. The document WO 96/18457 describes the use of these catalysts in dehydrogenation processes at moderate to high molar S/HC ratios of about 10.
The document EP-B 0 956 899 describes a dehydrogenation catalyst comprising iron oxide, potassium oxide, magnesium oxide, a further metal oxide and at least two rare earth metal oxides. Many further promoters can optionally be comprised, including, for example, MnO3. The addition of from 10 to 200 ppm of at least one titanium compound is not described in EP-B 0 956 899. The document EP-B 0 956 899 also describes the use of catalysts for the dehydrogenation of alkylaromatic compounds at a weight ratio of steam/hydrocarbon in the range from 0.5 to 2.5.
The document EP-A 0 502 510 relates to dehydrogenation catalysts comprising iron oxide, potassium oxide and from 0.005 to 0.95% by weight of titanium oxide as significant constituents. In addition, further promoters, in particular cerium oxide, molybdenum oxide or magnesium oxide, can be comprised. The addition of manganese is not described.
The document U.S. Pat. No. 4,220,560 describes a dehydrogenation catalyst comprising an iron-chromium spinel, which additionally comprises a further metal selected from among cobalt, zinc, manganese and magnesium. In addition, the use of the catalyst for the dehydrogenation of hydrocarbons at a molar steam/hydrocarbon ratio of from 9 to 12 is described. The addition of titanium is not described in the document U.S. Pat. No. 4,220,560.
The document US 2006/0106267 discloses a catalyst and its use for preparing styrene at a steam/hydrocarbon weight ratio of less than or equal to 1.35. The catalyst described in the document US 2006/0106267 comprises iron oxide together with a cerium compound, a potassium compound, a molybdenum compound, an alkaline earth metal compound and a small proportion of titanium dioxide. Apart from titanium dioxide, further promoters can be comprised. The addition of from 0.7 to 10% by weight of a manganese compound is not described. The document US 2006/0106:267 states that a styrene catalyst having a very low titanium content should have the greatest stability.
The document WO 99/49966 describes a catalyst which comprises iron oxide, potassium oxide, a magnesium compound and a cerium compound and has an iron-potassium phase, and also its use in the dehydrogenation of ethylbenzene. No catalyst comprising a titanium compound and from 0.7 to 10% by weight of a manganese compound is described.
The addition of manganese to dehydrogenation catalysts based on iron oxide is described, for example, in the publications Miyakoshi et al. (Appl. Cat. A 216, 2001, pp. 137-146) and Kotarba et al. (J. Cat. 221, 2004, pp. 650-652). Miyakoshi et al. describe a sol-gel process for producing an iron oxide dehydrogenation catalyst, with an MnFe2O4 spinel being said to be formed in the catalyst. Kotarba et al. describe a manganese-doped iron oxide catalyst comprising an active K2Fe22O34 ferrite phase, with the loss of potassium from the catalyst being said to be reduced by means of the manganese doping.
The document Liao et al. (Cat. Comm. 9, 2008, pp. 1817-1821) describes the influence of the addition of titanium dioxide on the structure and reactivity of an iron oxide dehydrogenation catalyst. An iron-potassium dehydrogenation catalyst to which from 1000 to 15 000 ppm of titanium dioxide have been added is described.
None of the documents discloses a positive effect of manganese in combination with titanium in a dehydrogenation catalyst comprising an iron compound, a potassium compound and a cerium compound. In addition, none of the documents discloses a positive effect of manganese and/or titanium on the catalytic performance at a low molar steam/hydrocarbon ratio of less than 7.35 (mol/mol).
There is a need for further-improved dehydrogenation catalysts for the dehydrogenation of hydrocarbons, which catalysts have increased stability at improved or equal catalyst activity and thus higher operating lives. It is an object of the present invention to provide an improved dehydrogenation catalyst based on iron oxide which displays, in particular, improved stability and/or an improved catalyst activity.
A further object of the present invention is to provide improved dehydrogenation catalysts which display better stability and/or activity than the catalyst compositions of the prior art in dehydrogenation processes at a low steam/hydrocarbon ratio (S/HC ratio), i.e. in particular at molar S/HC ratios of less than or equal to 7.35.
Likewise, a satisfactory mechanical stability of the catalyst and resistance to boiling water should be ensured. In addition, the production of the dehydrogenation catalyst should be able to be carried out simply and inexpensively, and in particular no complicated process steps, for example a sol-gel process, and/or high calcination temperatures should be necessary in the production of the catalyst.
It has now surprisingly been found that dehydrogenation catalysts comprising from 0.7 to 10% by weight of a manganese compound can be used advantageously, i.e. with a satisfactory operating life and high yields, in dehydrogenation processes at a low S/HC ratio (molar S/HC ratio of less than or equal to 7.35, in particular less than or equal to 6).
It has also been found that the promoting effect of manganese can, in particular, be increased by addition of small amounts of titanium in dehydrogenation catalysts comprising iron oxide, a potassium compound, a cerium compound and a manganese compound. In this context, it has been possible to determine an optimal amount of titanium. It has been found that the promoting effect of manganese can be changed into an inhibiting effect when the amount of titanium is increased.
The invention provides a dehydrogenation catalyst comprising at least one iron compound, at least one potassium compound, at least one cerium compound, from 0.7 to 10% by weight, preferably from 0.7 to 5% by weight, particularly preferably from 0.7 to 3% by weight, in particular from 0.7 to 2% by weight, in particular from 1 to 2% by weight, of at least one manganese compound, calculated as MnO2, and from 10 to 200 ppm, preferably from 30 to 150 ppm, particularly preferably from 50 to 120 ppm, in particular from 60 to 100 ppm, very particularly preferably from 60 to 80 ppm, of at least one titanium compound, calculated as TiO2.
Unless indicated otherwise, all the following figures in % by weight are based on the total dehydrogenation catalyst and are in each case calculated for the metal oxide in the highest oxidation state. For the purposes of the present invention, ppm means milligram per kilogram (mg/kg).
The catalysts of the invention display an improved activity and stability compared to the catalysts described in the prior art. In particular, the catalysts of the invention display improved properties in dehydrogenation processes at a low steam/hydrocarbon ratio (S/HC ratio), i.e. at molar S/HC ratios of less than or equal to 7.35. This improved activity at a low S/HC ratio is also reflected, for example, in a reduced decrease in the activity compared to known catalysts when a change is made from moderate to low S/HC ratios.
The expression “dehydrogenation catalyst comprising at least one iron compound, at least one potassium compound, at least one cerium compound and at least one manganese compound and optionally further metal compounds” means, for the purposes of the present invention, that the corresponding metals can be determined in the optionally indicated amounts in the catalyst. Mixed phases (e.g. oxide mixed phases) and/or isolated phases of the metal compounds described below can typically be present in the catalyst. It is also possible for one or more of the component(s) described below to be comprised, partly or completely, in another raw material used in production of the catalyst.
According to the invention, the dehydrogenation catalyst comprises at least one iron compound or at least one iron compound is used in the production of the dehydrogenation catalyst. The at least one iron compound is preferably an iron oxide, in particular Fe2O3.
The at least one iron compound is preferably selected from among natural or synthetic iron oxides and/or iron oxide hydroxides. In particular, the at least one iron compound is selected from the group consisting of a-Fe2O3 (hematite), y-Fe2O3, iron oxide hydroxide (e.g. α-FeOOH, goethite) and Fe3O4 (magnetite). As synthetic iron oxides, it is possible to use, for example, iron oxides which have been prepared by thermal decomposition of iron salt solutions.
In particular, the at least one iron compound and the at least one potassium compound can be present in the form of a potassium ferrite phase KxFeyOz, (where x=1; 2, y=1-22 and z=2-34).
Preference is given to using α-Fe2O3 (hematite) as iron compound. The use of α-Fe2O3 (hematite) in combination with goethite (FeOOH) and/or magnetite (Fe3O4) as iron compound is also preferred. The proportion of goethite (FeOOH) and/or magnetite (Fe3O4) is then typically from 0 to 30% by weight (based on the total amount of iron compound).
The specific surface area of the iron compound (e.g. as determined by the BET method) is typically in the range from 1 to 50 m2/g, preferably from 1 to 20 m2/g.
The at least one iron compound is typically comprised in an amount in the range from 50 to 90% by weight, preferably from 60 to 80% by weight, particularly preferably from 65 to 75% by weight, calculated as Fe2O3, in the dehydrogenation catalyst (based on the total weight of the dehydrogenation catalyst).
According to the invention, the catalyst comprises at least one potassium compound or at least one potassium compound is used in the production of the dehydrogenation catalyst. The at least one potassium compound is preferably selected from among potassium oxide, potassium carbonate, potassium hydroxide, potassium hydrogencarbonate, potassium oxalate and potassium ferrite, in particular selected from among potassium oxide, potassium carbonate, potassium hydroxide and potassium hydrogencarbonate. The at least one potassium compound is in particular a potassium oxide (K2O) or a mixed oxide. It is also possible to use another thermally decomposable potassium compound. The at least one potassium compound can typically be present in the catalyst as oxide mixed phase with the metals present in the catalyst.
The at least one potassium compound is typically comprised in an amount in the range from 1 to 30% by weight, preferably from 5 to 25% by weight, in particular from 10 to 15% by weight, in the dehydrogenation catalyst (based on the total weight of the dehydrogenation catalyst and calculated as K2O).
According to the invention, the dehydrogenation catalyst comprises at least one cerium compound or at least one cerium compound is used in the production of the dehydrogenation catalyst.
The at least one cerium compound is preferably selected from among cerium oxides, cerium hydroxides, cerium carbonates, water-comprising cerium carbonate and cerium oxalates. Preference is given to using mixtures of the cerium compounds mentioned. The at least one cerium compound is preferably selected from among cerium(IV) oxide (CeO2), cerium(III) oxalate and cerium(III) carbonate, preferably from among cerium(IV) oxide (CeO2) and cerium(III) carbonate. The at least one cerium compound is typically converted into cerium dioxide in the production of the catalyst.
The dehydrogenation catalyst preferably comprises from 2 to 20% by weight, preferably from 5 to 15% by weight, in particular from 5 to 10% by weight, of at least one cerium compound, calculated as CeO2. According to the invention, the catalyst comprises from 0.7 to 10% by weight of at least one manganese compound, calculated as MnO2; or at least one manganese compound is used in the amount indicated in the production of the dehydrogenation catalyst. The at least one manganese compound is preferably selected from among manganese oxides (e.g. MnO, Mn2O3, MnO2, Mn3O4), manganese carbonates and permanganates. The at least one manganese compound is particularly preferably selected from the group consisting of MnO, Mn2O3, MnO2 (e.g. pyrolusite), Mn3O4 and Mn2O7. In particular, the at least one manganese compound is a manganese oxide, in particular MnO2.
The at least one manganese compound is preferably added as manganese dioxide (MnO2) in the production of the catalyst. However, it is also possible to use other oxides of manganese or else other manganese compounds which decompose thermally. Furthermore, it is possible for the at least one manganese compound to be comprised partially or completely in another raw material used in production of the catalyst, e.g. in the iron oxide.
The manganese comprised in the catalyst is preferably not present in the form of a manganese-iron mixed oxide. At least 80% by weight, preferably at least 90% by weight, (based on the total amount of manganese) of the manganese comprised in the catalyst is preferably not present in the form of a manganese-iron mixed oxide. The manganese in the present catalyst preferably partly or virtually completely forms an independent manganese oxide phase. It is also possible for the manganese comprised in the catalyst to be partly or virtually completely present in the form of a manganese-potassium mixed oxide phase.
According to the invention, the dehydrogenation catalyst comprises from 0.7 to 10% by weight, preferably from 0.7 to 5% by weight, particularly preferably from 0.7 to 3% by weight, in particular from 0.7 to 2% by weight, in particular from 1 to 2% by weight, of at least one manganese compound, calculated as MnO2 (based on the total catalyst).
According to the invention, the dehydrogenation catalyst comprises from 10 to 200 ppm, preferably from 30 to 150 ppm, particularly preferably from 50 to 120 ppm, in particular from 60 to 100 ppm, very particularly preferably from 60 to 80 ppm, of at least one titanium compound, calculated as TiO2, or at least one titanium compound is used in the production of the dehydrogenation catalyst.
For the purposes of the present invention, ppm is milligram per kilogram (mg/kg).
The at least one titanium compound can, in particular, be selected from among titanium oxides, titanium alkoxides and titanium carboxylates. The at least one titanium compound is preferably titanium dioxide (TiO2). The at least one titanium compound is preferably added as titanium dioxide (TiO2) in the production of the catalyst. However, it is also possible to use other titanium compounds. Furthermore, it is possible for the at least one titanium compound to be comprised partly or completely in another raw material used in production of the catalyst, e.g. in the iron oxide.
It has been found that it is possible to produce a catalyst having particularly advantageous properties by means of, in particular, the combination of the at least one manganese compound and the at least one titanium compound, with, in particular, a synergistic effect being observed in respect of improved activity and yield. The addition of from 10 to 200 ppm of at least one titanium compound, calculated as TiO2, has been found to be particularly advantageous. In addition, it has been found that the addition of titanium without the addition of manganese brings about a significantly smaller improvement in the catalyst activity.
A preferred embodiment of the present invention therefore provides a dehydrogenation catalyst comprising from 0.7 to 10% by weight, preferably from 0.7 to 5% by weight, particularly preferably from 0.7 to 3% by weight, in particular from 0.7 to 2% by weight, in particular from 1 to 2% by weight, of at least one manganese compound, calculated as MnO2, and from 10 to 200 ppm, preferably from 30 to 150 ppm, particularly preferably from 50 to 120 ppm, in particular from 60 to 100 ppm, very particularly preferably from 60 to 80 ppm, of at least one titanium compound, calculated as TiO2.
In a particularly preferred embodiment, the present invention provides a dehydrogenation catalyst comprising from 0.7 to 3% by weight of at least one manganese compound, calculated as MnO2, and from 50 to 120 ppm of at least one titanium compound, calculated as TiO2.
In a particularly preferred embodiment, the present invention provides a dehydrogenation catalyst comprising from 0.7 to 2% by weight of at least one manganese compound, calculated as MnO2, and from 60 to 100 ppm of at least one titanium compound, calculated as TiO2.
In a preferred embodiment, the present invention relates to a dehydrogenation catalyst as described above, comprising:
In a preferred embodiment, the abovementioned components add up to 100% by weight.
The further components can be comprised (or be added) in amounts of from 0 to 30% by weight, preferably from 0 to 20% by weight, more preferably from 0.001 to 10% by weight, in particular from 0.1 to 5% by weight, in particular from 0.5 to 5% by weight.
The dehydrogenation catalyst can preferably comprise at least one compound selected from the group consisting of molybdenum (Mo), tungsten (W) and vanadium (V) as further component; or at least one such compound is added in the production of the dehydrogenation catalyst. The further component can, in particular, be selected from among oxygen compounds (for example oxides, oxide hydrates, oxo compounds) of molybdenum (Mo), tungsten (W) and vanadium (V). In particular, the at least one compound selected from the group consisting of molybdenum (Mo), tungsten (W) and vanadium (V) is a compound which is decomposed thermally in the production of the dehydrogenation catalyst.
Preference is given to using at least one molybdenum compound selected from among molybdenum oxides and molybdates (e.g. ammonium molybdate, potassium molybdate) as at least one further component. The at least one molybdenum compound is preferably ammonium heptamolybdate.
The dehydrogenation catalyst preferably comprises from 0.1 to 10% by weight, preferably from 1 to 5% by weight, of at least one compound selected from the group consisting of molybdenum, tungsten and vanadium, calculated as oxide in the respective highest oxidation state, as further component.
In particular, the dehydrogenation catalyst comprises from 0.1 to 10% by weight, preferably from 1 to 5% by weight, of at least one molybdenum compound, calculated as MoO3, as further component.
Furthermore, the dehydrogenation catalyst can comprise from 0 to 10% by weight, particularly preferably from 1 to 5% by weight, of at least one vanadium compound, calculated as V2O5.
The dehydrogenation catalyst preferably comprises at least one alkaline earth metal compound as further component, or at least one alkaline earth metal compound is used in the production of the dehydrogenation catalyst. In particular, the dehydrogenation catalyst can comprise from 0.1 to 10% by weight, preferably from 1 to 5% by weight, of at least one alkaline earth metal compound, calculated as oxide, as further component.
In a preferred embodiment, the dehydrogenation catalyst comprises at least one magnesium compound as further component. The dehydrogenation catalyst preferably comprises from 0.1 to 10% by weight, preferably from 1 to 5% by weight, of at least one magnesium compound, calculated as MgO, as further component. In particular, the at least one magnesium compound is selected from among magnesium oxide, magnesium carbonate (e.g. magnesite) and magnesium hydroxide. The at least one magnesium compound is preferably magnesium oxide (MgO) and/or magnesium carbonate (MgCO3) (e.g. magnesite). Preference is given to using magnesium oxide (MgO) and/or magnesium carbonate (MgCO3) (e.g. magnesite) as further component in the production of the catalyst.
In a preferred embodiment, the dehydrogenation catalyst comprises at least one calcium compound as further component. The dehydrogenation catalyst preferably comprises from 0.1 to 10% by weight, preferably from 1 to 5% by weight, of at least one calcium compound, calculated as CaO, as further component. In particular, the at least one calcium compound is selected from among calcium oxide, calcium carbonate and calcium hydroxide. The at least one calcium compound is preferably calcium oxide (CaO). Preference is given to using calcium oxide (CaO) and/or calcium hydroxide (Ca(OH)2) as further component in the production of the catalyst.
In a preferred embodiment, the dehydrogenation catalyst comprises at least one magnesium compound and at least one calcium compound. In particular, the dehydrogenation catalyst comprises from 0.1 to 10% by weight, preferably from 1 to 5% by weight, of at least one magnesium compound, calculated as MgO, and from 0.1 to 10% by weight, preferably from 1 to 5% by weight, of at least one calcium compound, calculated as CaO.
In a preferred embodiment, the above-described dehydrogenation catalyst comprises, as further components:
In a further preferred embodiment, the above-described dehydrogenation catalyst comprises, as further components:
Furthermore, the dehydrogenation catalyst can comprise one or more of the customary compounds for increasing the activity and/or selectivity, for example compounds selected from among Cr, Co, Ni, Cu, Zn, Al, Ga, Ge, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, Hf, Ta, Re, Ir, Pt, Au, Pb and Bi, as at least one further component (as promoter or dopant). The abovementioned customary promoters can typically be comprised in amounts of from 0 to 10% by weight, preferably from 0.001 to 5% by weight, preferably from 0.01 to 2% by weight.
In an embodiment, the above-described dehydrogenation catalyst comprises at least one further rare earth metal compound apart from cerium, in particular selected from the group consisting of lanthanum (La), praseodymium (Pr) and neodymium (Nd), as further component. The dehydrogenation catalyst preferably comprises from 1 to 1000 ppm, preferably from 10 to 500 ppm, particularly preferably from 20 to 300 ppm, of at least one further rare earth metal compound apart from cerium, calculated as oxide in the respective highest oxidation state. In particular, the catalyst comprises from 1 to 1000 ppm, preferably from 10 to 500 ppm, particularly preferably from 20 to 300 ppm, of at least one rare earth metal compound selected from the group consisting of lanthanum, praseodymium and neodymium. The dehydrogenation catalyst can preferably comprise from 1 to 1000 ppm, preferably from 3 to 500 ppm, particularly preferably from 10 to 100 ppm, of at least one lanthanum compound, calculated as La2O3, as further component. The dehydrogenation catalyst can preferably comprise from 1 to 1000 ppm, preferably from 3 to 500 ppm, particularly preferably from 10 to 100 ppm, of at least one praseodymium compound, calculated as PrO2, as further component. The dehydrogenation catalyst can preferably comprise from 1 to 1000 ppm, preferably from 3 to 500 ppm, particularly preferably from 10 to 100 ppm, of at least one neodymium compound, calculated as Nd2O3, as further component.
The above-described dehydrogenation catalyst can preferably comprise at least one compound of metals of transition groups 8 to 12 of the Periodic Table of the Elements as further component. The above-described dehydrogenation catalyst preferably comprises at least one compound of metals selected from the group consisting of ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au) and zinc (Zn); preferably selected from the group consisting of cobalt (Co), nickel (Ni), palladium (Pd), copper (Cu), and zinc (Zn); particularly preferably selected from the group consisting of nickel (Ni), copper (Cu), and zinc (Zn), as further component. The above-described dehydrogenation catalyst can, in particular, comprise from 1 to 1000 ppm, preferably from 50 to 500 ppm, particularly preferably from 50 to 200 ppm, of at least one compound of metals of transition groups 8 to 12 of the Periodic Table of the Elements, in each case calculated as oxide in the highest oxidation state, as further component. In a preferred embodiment, the above-described dehydrogenation catalyst comprises from 1 to 1000 ppm, preferably from 50 to 500 ppm, particularly preferably from 50 to 200 ppm, of at least one compound of metals selected from the group consisting of nickel (Ni), copper (Cu), and zinc (Zn), in each case calculated as oxide in the highest oxidation state. The dehydrogenation catalyst can preferably comprise from 1 to 1000 ppm, preferably from 30 to 500 ppm, particularly preferably from 30 to 200 ppm, of at least one nickel compound, calculated as NiO, as further component. The dehydrogenation catalyst can preferably comprise from 1 to 1000 ppm, preferably from 10 to 200 ppm, particularly preferably from 30 to 100 ppm, of at least one copper compound, calculated as CuO, as further component. The dehydrogenation catalyst can preferably comprise from 1 to 1000 ppm, preferably from 1 to 500 ppm, particularly preferably from 10 to 100 ppm, of at least one zinc compound, calculated as ZnO, as further component.
In addition, the dehydrogenation catalyst can comprise at least one compound of elements of main group 4 of the Periodic Table of the Elements as further component. The above-described dehydrogenation catalyst preferably comprises at least one compound selected from the group consisting of silicon (Si), germanium (Ge), tin (Sn) and lead (Pb) compounds, preferably at least one silicon compound, as further component. In particular, the dehydrogenation catalyst comprises from 1 to 1000 ppm, preferably from 5 to 500 ppm, particularly preferably from 10 to 100 ppm, of at least one compound selected from the group consisting of silicon (Si), germanium (Ge), tin (Sn) and lead (Pb) compounds, calculated as oxide in the respective highest oxidation state. In an embodiment, the dehydrogenation catalyst described comprises from 1 to 1000 ppm, preferably from 5 to 500 ppm, particularly preferably from 10 to 100 ppm, of at least one silicon compound, calculated as SiO2.
The above-described dehydrogenation catalyst can typically comprise at least one nonmetal selected from among nonmetals of main groups 5 to 7 of the Periodic Table of the Elements, in particular selected from the group consisting of nitrogen, phosphorus, sulfur and chlorine, as nonmetal in addition to oxygen.
In a preferred embodiment, the dehydrogenation catalyst comprises:
In a preferred embodiment, the abovementioned components add up to 100% by weight.
In a preferred embodiment, the dehydrogenation catalyst comprises:
In a preferred embodiment, the abovementioned components add up to 100% by weight.
All figures in % by weight are based, unless indicated otherwise, on the total dehydrogenation catalyst. All figures in % by weight were, unless indicated otherwise, calculated as oxide of the metal concerned, in each case in the highest oxidation state.
In particular, the present invention provides an above-described dehydrogenation catalyst for the catalytic dehydrogenation of hydrocarbons at a molar steam/hydrocarbon weight ratio in the range from 3 to 7.35; preferably in the range from 4 to 7; in particular in the range from 5 to 6.
Furthermore, the present invention provides a process for producing a dehydrogenation catalyst as described above, which comprises the following steps:
The basic mode of operation in the production of dehydrogenation catalysts is known to those skilled in the art. The above-described dehydrogenation catalysts can be produced, for example, as described in WO 99/49966.
In the process for producing a dehydrogenation catalyst, preference is given to using the metal compounds and further components described above in connection with the dehydrogenation catalyst. In particular, the above-described iron compounds, potassium compounds, cerium compounds, manganese compounds and titanium compounds are used in the production of the dehydrogenation catalyst. The above-described, in particular, molybdenum compounds, vanadium compounds, magnesium compounds and calcium compounds can optionally be used in the production of the dehydrogenation catalyst. The above-described further metal compounds can optionally be used in the production of the catalyst, and preference is given to one or more of the further metal compounds being entirely or partly present in one of the raw materials used, in particular in the iron oxide and/or cerium carbonate.
As compounds and further components, it is possible to use compounds as they are present in the finished catalyst or compounds which are converted during the production process into compounds as are present in the finished catalyst.
In particular, the invention provides a process for producing a dehydrogenation catalyst as described, wherein an iron(III) oxide (Fe2O3) is used as at least one iron component. In particular, it is possible to use an iron oxide having the following composition, where the figures indicate the amount of the element or the compounds based on the total amount of iron oxide:
In particular, the invention provides a process for producing a dehydrogenation catalyst as described, wherein a potassium carbonate (K2CO3) is used as at least one potassium compound. In particular, it is possible to use a potassium carbonate having the following composition, where the figures indicate the amount of the element or the compounds based on the total amount of potassium carbonate:
In particular, the invention provides a process for producing a dehydrogenation catalyst as described, wherein a cerium(III) carbonate (CeCO3) is used as at least one cerium compound. In particular, it is possible to use a cerium carbonate having the following composition, where the figures indicate the amount of the element or the compounds based on the total amount of cerium carbonate:
In particular, the invention provides a process for producing a dehydrogenation catalyst as described, wherein manganese(IV) oxide (MnO2) is used as at least one manganese compound. In particular, it is possible to use a manganese dioxide having the following composition, where the figures indicate the amount of element or compound based on the total amount of manganese dioxide:
In particular, the invention provides a process for producing a dehydrogenation catalyst as described, wherein titanium dioxide (TiO2) is used as at least one titanium compound.
In particular, the invention provides a process for producing a dehydrogenation catalyst as described, wherein an ammonium heptamolybdate is used as at least one molybdate compound. In particular, it is possible to use an ammonium heptamolybdate having the following composition, where the figures indicate the amount of element or compound based on the total amount of ammonium heptamolybdate:
In particular, the invention provides a process for producing a dehydrogenation catalyst as described, wherein magnesium oxide (MgO) or calcium hydroxide (Ca(OH)2) or both is/are used as at least one alkaline earth metal compound. In particular, it is possible to use a magnesium oxide having the following composition:
In particular, it is possible to use a calcium hydroxide having the following composition:
The figures relate to the amount of element or compound based on the total amount of the raw material.
To produce the catalyst premix, the components (typically in the form of solid powders) are generally mixed and then mixed with a solvent, in particular water, optionally with addition of a binder. Mixing is preferably carried out by intimate mixing, e.g. by kneading, in a stirred vessel, Mix-Muller, mixer, kneader or extruder, preferably in a Mix-Muller, kneader or mixer.
Shaped catalyst bodies are then typically produced (e.g. by extrusion or pressing) from the catalyst premix obtained in this way and these are subsequently dried and optionally calcined.
The at least one iron compound, the at least one potassium compound, the at least one cerium compound, the at least one manganese compound and the at least one titanium compound (typically in the form of solid powders) are optionally firstly mixed with further metal compounds (in particular at least one alkaline earth metal compound, at least one molybdenum compound) and then mixed with the solvent and optionally at least one binder.
A solvent use is made of, in particular, water or a mixture of polar solvents (e.g. alcohols, esters) and water. As binder (also known as plasticizer), it is possible to use, for example, alginate, starch, carboxymethylcellulose, hydroxyethylcellulose and polyvinyl alcohol. The binders are typically used in the form of a solution in water.
The production of shaped catalyst bodies from the catalyst premix is typically carried out by extrusion or pressing (tablet pressing). Examples of shaped catalyst bodies are cylinders (pellets), rings, star bodies and honeycomb bodies. The production of shaped catalyst bodies from the catalyst premix obtained in step i) is preferably carried out by means of extrusion.
After shaping, the moist shaped bodies are typically dried at temperatures of from 50° C. to 500° C., preferably from 80 to 350° C. Drying can take place for example in a drying oven (e.g. on metal sheets), in a drying drum or on belt dryers.
The shaped catalyst bodies are preferably calcined at temperatures in the range from 500° C. to 1200° C., preferably from 750 to 1000° C., preferably from 800 to 900° C., in step iii). The calcinations is preferably carried out in a rotary furnace.
In a preferred embodiment, the above-described process of the invention for producing a dehydrogenation catalyst comprises the following steps:
The present invention preferably provides a process for producing a dehydrogenation catalyst as described above, wherein from 0.7 to 10% by weight of manganese dioxide (MnO2), preferably from 0.7 to 5% by weight, particularly preferably from 0.7 to 3% by weight, in particular from 0.7 to 2% by weight, in particular from 1 to 2% by weight, (based on the finished catalyst) of manganese dioxide (MnO2) and from 10 to 200 ppm, preferably from 30 to 150 ppm, particularly preferably from 50 to 120 ppm, in particular from 60 to 100 ppm, very particularly preferably from 60 to 80 ppm, (based on the finished catalyst) of titanium dioxide (TiO2), calculated as TiO2, are added in step i).
In a further aspect, the present invention provides a process for the catalytic dehydrogenation of a hydrocarbon, wherein a mixture of steam and at least one hydrocarbon is brought into contact with a dehydrogenation catalyst as described above. The hydrocarbon is preferably ethylbenzene.
In particular, the invention provides a process for the catalytic dehydrogenation of a hydrocarbon, wherein low steam/hydrocarbon ratios are used. The present invention preferably provides a process for the catalytic dehydrogenation of a hydrocarbon, wherein a mixture of steam and at least one hydrocarbon having a molar steam/hydrocarbon ratio in the range from 3 to 7.35; preferably in the range from 4 to 7; in particular in the range from 5 to 6, is used. In particular, the invention provides a process for the catalytic dehydrogenation of ethylbenzene to styrene, wherein a mixture of steam and ethylbenzene having a steam/hydrocarbon weight ratio in the range from 0.5 to 1.25; preferably from 0.7 to 1.2; in particular from 0.85 to 1.1; particularly preferably from 0.9 to 1.0, is used.
In a further aspect, the present invention provides a process for the catalytic dehydrogenation of a hydrocarbon, wherein a mixture of steam and at least one hydrocarbon having a molar steam/hydrocarbon ratio in the range from 3 to 7.35; preferably in the range from 4 to 7; in particular in the range from 5 to 6, is brought into contact with a dehydrogenation catalyst comprising
As regards the iron compound, the potassium compound, the cerium compound and the manganese compound, the above-described embodiments, in particular, apply.
The process of the invention using a dehydrogenation catalyst comprising at least one iron compound, at least one potassium compound, at least one cerium compound and from 0.7 to 10% by weight of at least one manganese compound gives an improved styrene yield at low S/HC ratios compared to known processes and dehydrogenation catalysts.
The process described can be the dehydrogenation of alkylaromatic or aliphatic hydrocarbons, preferably the dehydrogenation of alkylaromatic hydrocarbons. The process of the invention for the dehydrogenation of a hydrocarbon can be, for example, the dehydrogenation of ethylbenzene to styrene, of isopropylbenzene: to alpha-methylstyrene, of butene to butadiene or of isoamylene to isoprene. The hydrocarbon is preferably ethylbenzene.
Yields of from 40 to 80%, preferably from 50 to 75%, particularly preferably from 60 to 70%, based on the hydrocarbon used, are typically achieved per pass through the reactor in the catalytic dehydrogenation process of the invention. In particular, in the catalytic dehydrogenation of ethylbenzene, styrene yields of from 40 to 80%, preferably from 50 to 75%, particularly preferably from 60 to 70%, based on the ethylbenzene used, are achieved per pass through the reactor. The yields indicated are in mol %.
The process for the catalytic dehydrogenation of a hydrocarbon is typically carried out at temperatures of from 500 to 650° C. and pressures of from 0.2 to 2 bar absolute.
Furthermore, the present invention provides for the use of a dehydrogenation catalyst as described above for the catalytic dehydrogenation of a hydrocarbon, in particular an alkylaromatic or aliphatic hydrocarbon, preferably an alkylaromatic hydrocarbon. The invention preferably provides for the use of a dehydrogenation catalyst as described above for the catalytic dehydrogenation of a hydrocarbon at a molar steam/hydrocarbon ratio in the range from 3 to 7.35; preferably in the range from 4 to 7; in particular in the range from 5 to 6.
Furthermore, the present invention provides for the use of a dehydrogenation catalyst comprising
for the catalytic dehydrogenation of a hydrocarbon, in particular an alkylaromatic or aliphatic hydrocarbon, preferably an alkylaromatic hydrocarbon, particularly preferably ethylbenzene, at a molar steam/hydrocarbon ratio in the range from 3 to 7.35; preferably in the range from 4 to 7; in particular in the range from 5 to 6.
The figures are explained below:
The styrene yield in mol % is in each case reported as the molar amount of styrene produced based on the molar amount of ethylbenzene used.
The present invention is illustrated by the following examples.
An iron oxide Fl (alpha-Fe2O3, hematite) comprising 0.027% by weight of manganese (Mn), calculated as MnO2, and 28 ppm of titanium (Ti), calculated as TiO2, was used. The BET surface area of the iron oxide Fl was 11 m2/g.
Further components used were potassium carbonate, cerium carbonate, magnesium oxide, calcium hydroxide and ammonium heptamolybdate. The compositions of the raw materials used determined by means of elemental analysis are shown below, where the figures relate to the respective element or the respective compound based on the respective total raw material.
A catalyst A having the nominal oxide composition 72.7% by weight of Fe2O3, 13.6% by weight of K2O, 7.4% by weight of CeO2, 2.2% by weight of MgO, 2% by weight of CaO and 2.1% by weight of MoO3, 0.02% by weight of Mn02 and 20 ppm of TiO2 was produced.
For this purpose, the abovementioned pulverulent components were firstly mixed dry and then kneaded with addition of water and starch solution. The catalyst composition was extruded to give pellets having a diameter of 3 mm and dried at 120° C. for 1 hour. The shaped catalyst bodies (pellets) were subsequently calcined in air at 350° C. for 1 hour and 825° C. for 1 hour.
A catalyst was produced as described in example 1, but, in contrast to example 1, titanium dioxide (TiO2) was additionally added. The iron oxide F1 was used.
A catalyst B having the nominal oxide composition of 72.7% by weight of Fe2O3, 13.6% by weight of K2O, 7.4% by weight of CeO2, 2.2% by weight of MgO, 2% by weight of CaO, 2.1% by weight of MoO3, 0.02% by weight of MnO2 and 70 ppm (mg/kg) of TiO2 was obtained.
A catalyst C was produced without addition of MnO2 and TiO2 and using an iron oxide F2 (Fe2O3, hematite) comprising 0.025% by weight of manganese (Mn), calculated as MnO2, and a proportion of titanium of 195 ppm (mg/kg) (corresponds to 325 ppm of Ti, calculated as TiO2). The BET surface area of the iron oxide F2 was 2.3 m2/g.
The composition of the iron oxide F2 was determined by means of elemental analysis and is shown below, where the figures relate to the respective element or compound based on the total raw material.
The production of the catalyst was carried out as described in example 1 using further raw materials described in example 1.
A catalyst C having the nominal oxide composition 72.7% by weight of Fe2O3, 13.6% by weight of K2O, 7.4% by weight of CeO2, 2.2% by weight of MgO, 2% by weight of CaO, 2.1% by weight of MoO3, 0.02% by weight of MnO2 and 240 ppm of TiO2 was obtained.
Example 4 Catalysts D-J (different additions of manganese) A series of catalysts D, E, F, G, H, I, J were produced with addition of various amounts of MnO2. The titanium content was set to a constant 70 ppm in these catalysts. An iron oxide F3 (Fe2O3, hematite), comprising 0.27% by weight of Mn (calculated as MnO2) and traces of Ti (<17 ppm as TiO2), was used here. The BET surface area of the iron oxide F3 was 1.2 m2/g.
Furthermore, potassium carbonate, cerium carbonate, magnesium oxide, calcium hydroxide, ammonium heptamolybdate, manganese dioxide and titanium dioxide were used in such amounts that catalysts having the actual oxide compositions as shown in table 1 were obtained. Unless indicated otherwise, the raw materials described in example 1 were used.
The compositions of iron oxide F3 and the manganese dioxide used were determined by means of elemental analysis and are shown below, where the figures relate to the respective element or the respective compound based on the respective total raw material.
The shaped catalyst bodies were produced as described in example 1.
A series of catalysts K, L, M, N were produced with addition of various amounts of TiO2. The manganese content was set to a constant 1.8% by weight (calculated as MnO2) in these catalysts. The iron oxide F3 (Fe2O3, hematite), comprising 0.27% by weight of Mn (calculated as MnO2) and no Ti (<17 ppm calculated as TiO2), described in example 4 was used here.
Furthermore, potassium carbonate, cerium carbonate, manganese oxide, calcium hydroxide, ammonium heptamolybdate, manganese dioxide and titanium dioxide were used in such amounts that catalysts having the actual oxide compositions as shown in table 1 were obtained.
The shaped catalyst bodies were produced as described in example 1. Unless indicated otherwise, the raw materials described in example 1 were used.
A catalyst 0 was produced with addition of 70 ppm of TiO2 and using an iron oxide F4 comprising no titanium (<17 ppm as TiO2) and 0.6% by weight of Mn (calculated as MnO2). The BET surface area of the iron oxide F4 was 1.1 m2/g. The production of the catalyst was carried out as described in example 2 with addition of TiO2 as titanium source. The further raw materials described in example 1 were used.
The composition of the iron oxide F4 was determined by means of elemental analysis and is shown below, where the figures relate to the respective element or the respective compound based on the total raw material.
Furthermore, potassium carbonate, cerium carbonate, manganese oxide, calcium hydroxide, ammonium heptamolybdate and titanium dioxide were used in such amounts that a catalyst having the nominal oxide composition 72.7% of Fe2O3, 13.6% of K2O, 7.4% of CeO2, 2.2% of MgO, 2% of CaO, 2.1% of MoO3, 0.5% by weight of MnO2 and 70 ppm of TiO2 was obtained. Unless indicated otherwise, the raw materials from example 1 were used.
The compositions of the catalysts were checked by means of elemental analysis and are shown in table 1.
The catalysts A to O from examples 1 to 6 were used in the dehydrogenation of ethylbenzene to styrene in the presence of steam. 13.3 ml of catalyst were installed in an isothermal tube reactor. At 620° C. and 1 atm outlet pressure, the catalyst was supplied continuously with 14.6 g/h of ethylbenzene and 14.6 g/h of deionized (DI) water, corresponding to an S/HC weight ratio of 1.0. After stabilization (after about 40 hours), the yield of styrene was determined by gas chromatography. The results in respect of ethylbenzene conversion, styrene selectivity and styrene yield for the various catalysts are shown in table 2 and
Ethylbenzene conversion, styrene selectivity and styrene yield were determined by means of the following formulae:
Conversion (mol %)=[(A*Mf−B*Mp)/(A*Mf)]×100
Selectivity (mol %)=[(D*Mp−C*Mf)/(A*Mf−B*Mp)]×(MEB/MST)×100
Yield (mol %)=conversion×selectivity/100
where:
The above figures in respect of concentration and molar masses are in each case based on the organic phase (without water).
The catalysts A to O from examples 1 to 6 were used in the dehydrogenation of ethylbenzene to styrene in the presence of steam, as described in example 7, with an S/HC weight ratio of 1.25 being set. 13.3 ml of catalyst were installed in an isothermal tube reactor. At 620° C. and 1 atm outlet pressure, the catalyst was supplied continuously with 14.6 g/h of ethylbenzene and 18.25 g/h of deionized (DI) water, corresponding to an S/HC weight ratio of 1.25.
The results in respect of ethylbenzene conversion, styrene selectivity and styrene yield for the various catalysts are shown in table 3. In addition, table 3 shows the decreases in the styrene yields when changing from an S/HC weight ratio of 1.25 to an S/HC weight ratio of 1.0 (delta Y 1.25→1.0).
The improved stability of the catalyst is additionally shown by a smaller loss of catalyst activity when changing from a medium to a low S/HC ratio (comparison of the results of examples 7 and 8).
The catalyst H was used in the dehydrogenation of 1-butene to butadiene. A volume of 38 ml of catalyst was used in an isothermally heated tube reactor. At 620° C. and 1 atm, the reactor was continuously supplied with 60 g/h of deionized water and 22.5 g/h of 1-butene (corresponding to a molar ratio of steam/butene of 8.6). After stabilization (about 16 hours), the product mixture obtained was analyzed by gas chromatography. The conversion of 1-butene and the butadiene selectivity were calculated using the formulae as in example 7, replacing ethylbenzene by 1-butene and styrene by butadiene. The butene conversion was 23.3 mol % and the butadiene selectivity was 91.2 mol %.
This application is a divisional application of U.S. Ser. No. 13/723,544, filed Dec. 21, 2012 which is a non-provisional application of U.S. Ser. No. 61/578,897, filed Dec. 22, 2011, all of which are incorporated herein by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61578897 | Dec 2011 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13723544 | Dec 2012 | US |
| Child | 15834460 | US |
