Catalyst Deactivation 1991


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All of these areas were well represented as attested by the substantial number of papers contained in these proceedings. Four review papers based on the plenary lectures provide state-of-the-art perspectives on new thrusts in deactivation research and development. Skip to content. Perusall turns often-skipped solitary reading assignments into engaging collective activities students don't want to miss.

Students collectively annotate each reading — asking questions, responding to each other's questions, or sharing other perspectives or knowledge. Perusall's novel data analytics automatically grade these annotations to ensure that students complete the reading, and as an instructor, you get a classroom of fully prepared students every time. The periodic slab model comprised a five-layer CeO 2 , a supercell with dimensions of The negative sign of Eads corresponds to the energy gain of the system due to ligand adsorption.

The spin-polarized first-principles total energy calculations are performed using an ultrasoft pseudopotential method. The system would gradually become relaxed to achieve a balanced state with convergent energy, when the forces on the relaxed atoms were less than 0. The relative energies of the initial state, transition state, and final state presented in this study were zero-point-energy obtained from frequency calculations at the same level of optimization. The energy convergence of the I.

Qiao, B. Yang, X. Single-atom catalysts: a new frontier in heterogeneous catalysis. Liu, L. Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles.

S David Jackson Research : CATALYST ACTIVATION/DEACTIVATION

Fu, Q. Active nonmetallic Au and Pt species on ceria-based water-gas shift catalysts. Science , — Hayashi, T. Hutchings, G.

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Catalysis by gold. Today , 55—61 Lee, J.


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Murdoch, M. Wittstock, A. Nanoporous gold catalysts for selective gas-phase oxidative coupling of methanol at low temperature. Conte, M. Hydrochlorination of acetylene using a supported gold catalyst: a study of the reaction mechanism. Vapor-phase hydrochlorination of acetylene - correlation of catalytic activity of supported metal chloride catalysts.

A golden age of catalysis: a perspective. A-GEN , 2—5 Nkosi, B. Hydrochlorination of acetylene using carbon-supported gold catalysts - a study of catalyst reactivation. Jayakrishnan, K. Immobile plasticizer in flexible PVC. Nature , — Lakshmi, S. Migration resistant, blood-compatible plasticized polyvinyl chloride for medical and related applications. Organs 22 , — Dan, N. Kinetics of gas-phase hydrochlorination of acetylene over a mercury catalyst.

Malta, G. Identification of single-site gold catalysis in acetylene hydrochlorination. Zhao, J. Activated carbon supported ternary gold-cesium I -indium III catalyst for the hydrochlorination of acetylene. Zhu, M. Development of a heterogeneous non-mercury catalyst for acetylene hydrochlorination. ACS Catal. Huang, C. Li, G. Non-mercury catalytic acetylene hydrochlorination over activated carbon-supported Au catalysts promoted by CeO 2.

Zhou, K. A low content Au-based catalyst for hydrochlorination of C 2 H 2 and its industrial scale-up for future PVC processes. Johnston, P. Discovery, development, and commercialization of gold catalysts for acetylene hydrochlorination.

Zhang, H. Non-mercury catalytic acetylene hydrochlorination over activated carbon-supported Au catalysts promoted by CeO2. Haiyang, Z. Hydrochlorination of acetylene using gold catalysts - a study of catalyst deactivation. Zhong, J. Heterogeneous non-mercury catalysts for acetylene hydrochlorination: progress, challenges, and opportunities. Goguet, A. Increased dispersion of supported gold during methanol carbonylation conditions.

Wang, Y. Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles. Wolcyrz, M. Solid State Chem. Yang, Y. Redox enzyme-mimicking activities of CeO 2 nanostructures: intrinsic influence of exposed facets. Chang, S. RSC Adv. Pantelouris, A. Parsons, J. X-ray absorption near edge structure and extended X-ray absorption fine structure analysis of standards and biological samples containing mixed oxidation states, of chromium III and Chromium VI. Otto, K. Karnatak, R. Manifestation of localized and extended f-states in the 3d absorption-spectra.

B 36 , — Dexpert, H. Rare-earth valence state by liii absorption edges. Mai, H. Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes. B , — Chen, B. Catalytic removal of formaldehyde at room temperature over supported gold catalysts. Yang, Z. Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction.

ACS Nano 6 , — Ke, J. Rare Earths 35 , — Hoshiya, N. Sulfur modification of Au via treatment with piranha solution provides low-pd releasing and recyclable pd material, sapd. Thompson, S. Beamline I11 at Diamond: a new instrument for high resolution powder diffraction. Butikova, I. Crystal-structure of csnax-zeolite in hydrated and dehydrated forms. Thus they show that a NH4Y zeolite modified by the three-step treatment does exhibit a substantial increase in cracking activity whereas the sole steam treatment carried out under the same steaming conditions leads to a decrease thereof cf.

Table III, conversion and rate constant. Therefore this teaching does not hint at the possibility of improving the alpha-activity of a catalyst containing a ZSM-5 zeolite by subjecting it to carefully controlled steaming conditions and, in the Board's view, it would have led the skilled person away from the claimed solution. Document 5 is concerned with the selective ethylation of mono alkyl benzene in the presence of a catalyst comprising a matrix and a zeolite, such as ZSM-5, which has been subjected to a steam treatment within particular ranges of temperature, pressure and time cf.

Claims 14, 16 and 17; column 11, lines However the aim of this steam treatment is to reduce the cracking activity alpha of the zeolite from an initial alpha-value of greater than to less than , preferably between , in order to selectively produce the para or meta derivates of the mono alkyl benzene cf. This teaching would certainly not encourage the skilled person confronted with the opposite problem of increasing the alpha-activity of ZSM-5 containing catalysts to undertake further experimentation in connection with the steaming conditions.

The Board cannot follow the Respondent's arguments that in view of runs 4 and 5 in Table I, the skilled person would conclude to an improvement of the alpha-activity of the ZSM-5 by steaming. It is true that the toluene conversion is higher in run 5 than in run 4, however as pointed out by the Appellant the ethylene conversion has decreased so that no conclusion can be drawn as regards the alpha-value.

In the Board's view the teaching of Table 1 is consistent with the rest of the description, namely that the steam treatment improves the selectivity of the catalyst. The teaching of document 1 referred to in the decision under appeal is also that a steam treatment of zeolites such as ZSM-5 reduces their alpha-activity. Like document 6 , this document cannot be helpful to the skilled person whose aim is, on the contrary, to increase the alpha-value of the catalyst.

Document 9 already discussed above in connection with novelty is consistent with the teaching of the preceding documents as regards the effect of steam on zeolites, in particular on ZSM It clearly discloses the deactivation effect of steam on HZSM see page , right-hand column, last sentence and page left-hand column and Fig. In view of this teaching and as the high alpha-values reported in Table 3 cannot be construed as resulting from an activation of the zeolite by steaming see the reasons given above in point 3.

Document 14 was cited by the Respondent for the first time at a very late stage of the appeal procedure in order to refute the Appellant's contention that the effect of steaming to enhance the activity of zeolites is a new phenomena. In view of the fact that firstly this argument was itself put forward also for the first time at the appeal stage, secondly document 14 is a patent of the Appellant and thirdly it is of relevance for the present case, the Board has decided to take it into consideration Art.

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This document discloses a process for producing a hydrothermally stable Y zeolite of high hydrocarbon conversion activity which comprises calcining an NH4Y zeolite in the presence of rapidly flowing steam under a water vapour pressure of at least 0. Claim 6.

The tests carried out in example 2 demonstrate that the catalytic activity alpha increases and passes through a maximum as the humidity of the calcination atmosphere increases, the magnitude of this maximum depending upon the duration of the steam treatment cf.


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The question which arises is whether in view of this teaching about NH4Y the skilled person would have effected further experimentation as regards the steaming of a ZSM-5 containing catalyst in expectation of an increase in the alpha activity. These arguments were not contested by the Respondent who, on his part, cited 14 only to show that activation of zeolites by steaming was known without contending that the teaching about NH4Y would have been obviously transposable to ZSM Furthermore documents 9 , 5 and 1 all disclose a decrease in the alpha-value of ZSM-5 by steaming and the two curves illustrating the steam stability of HZSM-5 and HY in 9 cf.

Under these circumstances the Board concurs with the Appellant's opinion that the skilled person aware of the fundamental differences between these two types of zeolites would not expect in view of the teaching of 9 , 5 , 1 , 6 and 14 that steaming of ZSM-5 might lead to an activation thereof and therefore would not have been encouraged to carry out experimentation in this direction. For the preceding reasons, the subject-matter of Claim 1 is considered to involve an inventive step.

Claim 1 being allowable, the same applies to the dependent Claims whose patentability is supported by that of Claim 1. The Respondent has not raised any particular objection against the independent Claim 12 during the appeal procedure. This claim is construed by the Board as relating to a process for hydrocarbon conversion carried out in the presence of a catalyst activated by the method according to Claims 1 to 11, i. As this activated catalyst differs from the ZSM-5 zeolite of document 9 by the presence of the matrix, from that of 6 at least by a different surface structure and from the catalysts of 5 and 1 by a higher alpha-activity at comparable compositions, it is novel.

Furthermore this improved alpha-activity was unexpected in view of the teaching of the cited documents about the deactivation effect of steam upon acid ZSM-5 zeolites. Under these circumstances the activated catalyst as such would be regarded as inventive. Therefore its use in known hydrocarbon conversions is also considered as patentable and Claims are allowable. The Respondent's contention that the requirements of sufficiency of disclosure are not met cannot be followed by the Board.

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Thus, firstly the Respondent has brought no evidence that the skilled person was unable to repeat the examples of the patent or that activation of the catalyst cannot be achieved when carrying out the invention as described in the examples. Secondly the Appellant has admitted that an activation of the zeolite may have occurred under the steaming conditions of NH4 ZSM-5 disclosed at page of 9. Therefore there exists no reason for believing that the disclosure of the invention is insufficient. The case is remitted to the Opposition Division with the order to maintain the patent on the basis of Claim 1 filed during oral proceedings, Claims as granted with the amendments in Claim 11 received on 21 February and an adapted description.

You could be one of ten lucky winners of an EPO gym bag. See also Frequently asked questions about the Boards of Appeal. Board: 3. In support of his request, the Appellant argued essentially as follows: It was the basic assumption in the state of the art that hydrothermal treatment of zeolites tends to bring out loss of crystallinity and therefore also of structure-determined properties such as catalytic activity.

The main arguments put forward by the Respondent can be summarised as follows: The subject-matter of Claim 1 is not novel over the disclosure of document 9. The Respondent requests that the appeal be dismissed. Reasons for the Decision 1. The appeal is admissible.

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