Patent Application
20140336041
The invention relates to new catalysts and their use for the production of synthesis gas.
Since a few decades, increasing attention is being paid to the utilization of biomass derived products as renewable energy source. The interest is due to the possibilities to replace oil with a raw material, potentially leading to zero emission of carbon dioxide CO2 (20-20-20 Renewable Energy UE Directive, 23/01/08, concerning the European Energy Policy and the Kyoto's Protocol). Of great interest is the possibility to produce hydrogen and synthesis gas by ethanol and other oxygenated reforming to be used, as example, in high efficiency fuel cell [F. Aupretre et al., Catal. Communications (2002) (3) 263-267; J. Armor; Appl. Catal. A: General (1999), 176, 159; Dunn S.; Int J. Hydrogen Energy (2002), 27(3), 235-264].
Among the oxygenate compounds, ethanol is a good candidate for several reasons:
(i)—It is produced through carbohydrates fermentation;
(ii)—It could easily be decomposed in the presence of water to generate a hydrogen-rich mixture;
(iii)—It is free from catalyst poisons such as sulfur.
However, the presences of two carbon atoms and of oxygen lead possible several reactions. The reaction pathway are much more complex than that of methane and ethane partial oxidation and reforming and even more complex than that of methanol, therefore it is very important the role of the catalyst, of the support and their interaction able to select a specific reaction pattern maximizing the hydrogen selectivity at relatively low temperature [A. Haryanto et al.; Energy & Fuels (2005) 19, 2098-2106].
The reaction of steam reforming of ethanol is, from a thermodynamic point of view, feasible above 500 K and at low temperature. It is strongly endothermic in absence of oxygen.
Different catalytic system have been studied in this reaction using different metals and various supports, but often a low comprehension about the specificity of each material and the interaction with the support is reported. From these studies it can be evidenced that good catalysts for ethanol steam reforming are supported metals like Co, Ni, Rh, Ru, Pd, Ir and Pt. Most of them promote the dehydrogenation to acetaldehyde and prevent the dehydration to ethylene.
However, at a certain level of temperature, these metals decompose the organic substrate to C* and H* (dissociative adsorption), getting close to thermodynamic equilibrium and giving problems in the effective evaluation of the catalysts selectivity. The coke formation has very often been observed on the surface of the catalysts. The coke formation is even more problematic if the process is carried out with raw ethanol and/or high pressure. Both conditions not only are required for the development of an industrial process and outstanding scientific challenge. Therefore, using these conditions, the possibility to run a process at low temperature with a selective reaction pathway is determinant to inhibit the intermediate which are coke precursors. In particular, the presence of other oxygenated impurities in the raw ethanol (such as butanol or diethyl-ether) can form olefins and promote the coke formation. The study of these effects allows extend the results at different organic substrate of biological origin.
Although the formation of coke at low temperature is still a problem on this catalyst, it can be inhibited through the support modification and the metal support interaction. Recently, structured catalysts based in cobalt and zinc oxide supported on cordierite monoliths and macroporous silicon have been studied. The study of the reaction pathway and the reaction intermediates of the steam ethanol reforming revealed that ethanol and acetaldehyde compete for the same active sites and that water and methane conversion depend on ethanol conversion since water and methane, reaction intermediate, are adsorbed on the same active sites than ethanol. The nature of the active sites greatly modify the catalytic activity, in particular a support with both strong or weak acidic sites mainly favors the C—C breakage and therefore the formation of CO and CHx, while the presence of only acidic sites favors the acetaldehyde formation.
Few studies are focused on the combined effect of metal and support or the combination in bimetallic catalysts and several aspects of the process are still little understood. Nevertheless, the scientific community agrees that the control of activity and selectivity need to be faced through studies involving the preparation of materials able to tailor the metal support interaction and the chemical environment in the nano-structure. To obtain such materials it is necessary to develop a new approach allowing control the dispersion of the active phase from the first stages of the preparation leading to active sites strongly interacting with the support.
The innovative approach is related to the insertion of the noble metal inside a well defined crystalline structure prepared in the way to give rise to the noble metal dispersed, like in a solid solution, inside an oxide matrix. One of the most promising methods is related to the insertion of metallic cations of active phase inside an hydrotalcite type structure. Recent studies have demonstrated that it is possible to obtain a noble metal dispersed on the surface by a reduction process. Catalysts obtained with this method have shown to be active in the partial oxidation and steam reforming of methane to synthesis gas without strong deactivation during reaction conditions.
Certain embodiments of the invention are related to the possibility to obtain high activity, selectivity and stability of the Rh° obtained by reduction of specific phase distribution of mixed oxides in which the Rh3+ is present after calcination of hydrotalcite precursor. The catalysts are obtained from the hydrotalcite structure containing Rh, Mg, Al and having carbonate or silicate as interlayer anions and in the way to obtain a specific phase distribution and an high Rh dispersion after the high temperature reduction treatment.
Recent studies have demonstrated that it is possible to obtain a noble metal dispersed on the surface by a reduction process. Catalysts obtained with this method have shown to be active in the transformation of methane to synthesis gas without deactivation during reaction conditions. Nevertheless the activity of the best catalyst used in the methane reforming are not suitable catalyst in this reaction due to the metal support interaction, to the structure sensitiveness of the reaction and to the catalyst stability.
That is the reason why the invention concerns new catalysts with enhanced performances in terms of activity, selectivity and stability towards hydrogen and carbon monoxide formation, which are active in a wide range of temperature and which generates C2 by-products in a very low amount. These catalysts are based on hydrotalcite precursor containing rhodium, both using carbonate or silicate as interlayer anions and having a specific phase distribution after calcination and a high Rhodium dispersion after the high temperature reduction treatment. The catalysts are active and selective at low temperature (500° C.) with 100% selectivity in Cl products, with no formation of by product. The catalysts are active and stable at higher temperature and need low residence time reaching equilibrium value below 50 ms at 550° C.
According to a first embodiment the invention concerns an Hydrotalcite-like compound of the formula (I):
[RhxMgyAlw(OH)2](3x+2y+3w−2)+(A2−)(3x+2y+3w−2)/2,k H2) (I)
wherein:
According to a particular embodiment, in the formula (I) as hereinabove defined, 0.5≦y<0.9.
According to another particular embodiment, in the formula (I) as hereinabove defined, 0.1≦w≦0.4.
According to another particular embodiment, in the formula (I) as hereinabove defined, the atomic ratio: [y/(w+x)]≧2.
Examples of such Hydrotalcite-like compounds are those of the following formulas:
[Rh0.0055Mg0.6800Al0.3145(OH)2]0.32+(A2−)0.16k H2O,
[Rh0.0050Mg0.8000Al0.1950(OH)2]0.20+(A2−)0.10 k H2O,
[Rh0.0043Mg0.6800Al0.3157(OH)2]0.32+(A2−)0.16 k H2O,
[Rh0.0043Mg0.8000Al0.1957(OH)2]0.20+(A2−)0.10 k H2O.
According to more particular embodiment, hydrotalcite-like compounds are those of the following formulas:
[Rh0.0043Mg0.6800Al0.3157(OH)2]0.32+(CO32−)0.16 k H2O,
[Rh0.0043Mg0.8000Al0.1957(OH)2]0.20+(SinO2n+12−)0.1 k H2O.
The invention relates to a synthesis process of the Hydrotalcite-like compound of the formula (I) hereinabove defined, comprising the following steps:
The synthesis process as hereinabove defined may further comprise:
The invention also relates to a synthesis process of a catalyst comprising :
The synthesis process of a catalyst as herein above defined, may further comprises :
According to another embodiment, the invention concerns a catalyst consisting in a combination of rhodium (Rh), magnesium oxide (MgO), mixed magnesium and aluminium oxide (MgAl2O4), and optionally mixed magnesium and silicon oxide (Mg2SiO4), and obtainable by the process as hereinabove defined, wherein:
The invention also concerns a synthesis process for the preparation of the catalyst as hereinabove defined, comprising the following steps:
The invention also concerns the use of said catalysts, as a catalyst for hydrocarbons reforming and/or as a catalyst for ethanol reforming.
The following paragraphs disclose non-limitative examples of catalysts according to the present invention.
The invention is related to the preparation of an active selective and stable catalyst, by insertion of metallic cations as active phase inside an hydrotalcite type precursor, from which the catalyst can be obtained by calcination at a temperature between 750° C. and 1000° C. and reduction between 700 and 900° C.
These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the invention and are therefore not to be considered limiting of the invention's scope as it can admit to other equally effective embodiments.
Surprisingly among the four catalysts prepared with 1.0 wt. % of Rh the catalyst obtained by calcination and reduction of the Rh/Mg/Al 0.5/80/19.5 a.r. hydrotalcite with silicate as interlayer anion (RO5M80A) and the Rh/Mg/Al 0.43/68/31.57 a.r. with carbonate (R043MA) are active and selective while the catalyst obtained by hydrotalcite with Rh/Mg/Al/0.55/68/31.45 with carbonate as interlayer (R055MA) is poorly selective while the Rh/Mg/Al 0.43/80/19.5 with silicate as interlayer anion (R043M80A) is poorly active and selective towards hydrogen and synthesis gas.
The composition of hydrotalcites is summarized in the following
The activity and selectivity of the 4 hydrotalcite (HT)-derived catalysts are reported in
The selectivity is maximum in the synthesis gas product and minimum in C2 and C3 products, which are coke precursors. In fact, no carbon formation on the catalysts has been observed at low C2+ selectivity.
Even more clearly are the specificity of the two R043MA and RO5M80A catalysts if the catalyst selectivities are compared at similar conversion.
The selectivity in hydrogen is reported in
The diffraction patterns of the calcined catalysts (
The hypothesis of the phase composition of the matrix containing the active phase are summarized in
The previous catalysts have been tested at temperature between 500 and 600° C. showing optimal stability with time on stream. The tests carried out for a period of 65h demonstrate the stability of the performances of the RO5M8OS with time on stream even using Surfin grade ethanol (commercial grade). The tests show an increase of the methane conversion and Hydrogen selectivity while the ethanol conversion is maintained to 100%.
While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. Furthermore, if there is language referring to order, such as first and second, it should be understood in an exemplary sense and not in a limiting sense. For example, it can be recognized by those skilled in the art that certain steps can be combined into a single step.
The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise.
“Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” as used herein may be replaced by the more limited transitional terms “consisting essentially of” and “consisting of” unless otherwise indicated herein.
“Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary a range is expressed, it is to be understood that another embodiment is from the one.
Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.
Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such particular value and/or to the other particular value, along with all combinations within said range.
All references identified herein are each hereby incorporated by reference into this application in their entireties, as well as for the specific information for which each is cited.
| Number | Date | Country | Kind |
|---|---|---|---|
| 11306723.5 | Dec 2011 | EP | regional |
This application is a §371 of International PCT Application PCT/EP2012/072602, filed Nov. 14, 2012, which claims the benefit of EP11306723.5, filed Dec. 21, 2011, both of which are herein incorporated by reference in their entireties.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2012/072602 | 11/14/2012 | WO | 00 | 6/19/2014 |
