HYDROCARBON CONVERSION PROCESS AND CATALYST COMPOSITION

Abstract: Process for the preparation of an olefins-containing mixture of hydrocarbons, which process comprises contacting a hydrocarbonaceous feedstock with a zeolitic catalyst at a temperature above 480 DEG C during less than 10 seconds, whereby the zeolitic catalyst comprises a mixture of a zeolite I and a zeolite II in a matrix, wherein zeolite I has a pore diameter of 0.3 to 0.7 mn and zeolite II has a pore diameter greater than 0.7 nm, and wherein the catalyst contains at least 25 % by weigth of zeolitic material. The invention further relates to a catalyst composition comprising a mixture of a zeolite I and a zeolite II in a matrix material, wherein zeolite I has a pore diameter of 0.3 to 0.7 nm, zeolite II has a pore diameter greater than 0.7 nm, and the composition contains at least 25 % by weight of zeolitic material.

Description: HYDROCARBON CONVERSION PROCESS AND CATALYST COMPOSITION The present invention relates to processes for the preparation of an olefins-containing mixture of hydrocarbons and to catalyst compositions which can be used in such processes. There is considerable interest in the production of olefins, especially ethylene and propylene, as their reactivity renders them suitable for conversion to further products, in contrast to the low value lower paraffins. Ethylene and propylene are valuable starting materials for chemical processes, while C, olefins can find use as a starting material for alkylation and/or oligomerization procedures in order to produce high octane gasoline and/or middle distillates. Isobutene can be usefully converted to methyl t-butyl ether. It is known to convert hydrocarbonaceous feedstocks, such as light distillates, to products rich in lower olefins, especially ethylene and propylene, by high temperature steam cracking. The typical product slate obtained in such steam cracking processes is not entirely suited to the needs of the chemical industry in that it represents a relatively high methane production level and a high ratio of ethylene to propylene. There have recently been developed alternative processes for the production of lower olefins, for example as described in EP 0347003, EP 0392590 and EP 0385538, from a wide range of hydro- carbonaceous feedstocks. Those processes have been found to give surprisingly high yields of lower olefins, low amounts of methane and a low ratio of ethylene to propylene and C, olefins when compared with conventional steam cracking. It has now been found that under comparative reaction conditions very attractive product slates can be obtained in terms of both lower olefins and gasoline yields when use is made of a specific zeolitic catalyst. Accordingly, the present invention relates to a process for the preparation of an olefins-containing mixture of hydrocarbons, which process comprises contacting a hydrocarbonaceous feedstock with a zeolitic catalyst at a temperature above 480 °C during less than 10 seconds, whereby the zeolitic catalyst comprises a mixture of a zeolite I and a zeolite II in a matrix material, wherein zeolite I has a pore diameter of 0.3 to 0.7 nm and zeolite II has a pore diameter greater than 0.7 nm, and wherein the catalyst contains at least 25% by weight of zeolitic material. In this way high yields of lower olefins and gasoline and relatively low yields of cycle oils can be obtained. Moreover, the gasoline obtained has an attractive octane number. Suitably, the catalyst composition comprises an intimate mixture of the zeolites I and II in a porous matrix material. The above implies that a catalyst particle of the catalyst composition according to the present invention contains both zeolites. It may be expected that the use of an intimate mixture of two zeolites such as zeolites I and II of the present invention in a porous matrix material would result in an unacceptable loss in conversion over that of a catalyst containing only zeolite II when operating at identical catalyst/oil ratio and contact time, due to the dilution in zeolite II with respect to feedstock, i.e. the lower zeolite Il/oil ratio in the catalyst of the invention than in a conventional zeolite II catalyst. It has now surprisingly been found that in a process of the invention use of a catalyst containing at least 25% by weight of zeolitic material results in a greater conversion when operated at identical catalyst/oil ratio, than in a process using catalyst containing only zeolite II. Preferably, the zeolitic catalyst contains at least 30% by weight of zeolitic material. The zeolitic catalyst can suitably contain up to no less than 50% by weight of zeolitic material. The zeolitic catalyst to be used in the process according to the present invention suitably has a zeolite I/zeolite II weight ratio ranging from 0.01 to 10, preferably from 0.2 to 3. The zeolite I has a pore diameter of 0.3 to 0.7 nm, preferably of 0.5 to 0.7 nm. Suitable zeolites I include crystalline silica (silicalite) , silicoaluminophosphates (SAPO) , chromosilicates, gallium silicates, iron silicates, aluminium phosphates (ALPO) , titanium aluminosilicates (TASO) , boron silicates, titanium aluminophosphates (TAPO) and iron aluminosilicates. Examples of zeolite I include SAPO-4 and SAPO-11, which are described in US-A-4,440,871, ALPO-11, described in US-A-4,310,440, TAPO-11, described in US-A-4,500,651, TAS0-45 described in US-A-4,254,297, aluminium silicates like erionite, ferrierite, theta and the ZSM-type zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-23, and ZSM-38. Preferably the zeolite I is selected from the group consisting of crystalline (metallo)silicates having a ZSM-5 structure, ferrierite, erionite and mixtures thereof. Suitable examples of crystalline (metallo)silicates with ZSM-5 structure are aluminium, gallium, iron, scandium, rhodium and/or chromium silicates as described in e.g. GB-B-2,110,559. After the preparation of the zeolite I usually a significant amount of alkali metal oxide is present in the readily prepared zeolite. Preferably, the amount of alkali metal is removed by methods known in the art, such as ion-exchange, optionally followed by calcination, to yield the zeolite in its hydrogen form. Preferably, the zeolite I is substantially in its hydrogen form. Suitably, zeolite I has an average crystallite size of less than 2 micrometer. Preferably, zeolite I to be applied in the process according to the present invention has an average crystallite size of less than 1 micrometer. More preferably, zeolite I has an average crystallite size in the range from 0.01 to 0.5 micrometer. The term crystallite size in this specification is to be regarded as the size of the individual zeolite crystals. These individual crystals may agglomerate into clusters which each may comprise 3 to 10 or more individual crystals. Preferably, zeolite I comprises individual crystals. The zeolite II has a pore diameter greater than 0.7 nm. Suitable zeolites II include the faujasite-type zeolites, zeolite beta and zeolite omega. Fauj site-type zeolites, including zeolites X and Y, are preferred; in particular zeolite Y is preferred. The zeolite can be in its acidic form, i.e. the form in which the zeolite hardly contains any alkali metal ions. In an especially preferred embodiment zeolite I comprises ZSM-5 and zeolite II comprises zeolite Y. The matrix material suitably comprises an inorganic oxide. Suitable matrix materials include alumina, silica, silica-alumina, magnesia, titania, zirconia, natural or synthetic clays, like kaolin, and mixtures thereof. The hydrocarbonaceous feedstock is contacted with the zeolitic catalyst for less than 10 seconds. Suitably, the minimum contact time is 0.1 second. Very good results are obtained when the hydro- carbonaceous feedstock is contacted with the zeolitic catalyst during 0.2 to 6 seconds. The process is carried out at a relatively high temperature. It is the combination of high temperature, short contact time and use of the specific catalyst composition which allows the high conversion to lower olefins and gasoline obtained. A preferred temperature range is 480 to 900 "C, more preferably 500 to 800 °C. The pressure to be used in the process according to the present invention can be varied within wide ranges. It is, however, preferred that the pressure is such that at prevailing temperature the mixture of hydrocarbons obtained is substantially in its gaseous phase or brought thereto by contact with the catalyst. This can be advantageous since no expensive compressors and high- pressure vessels and other equipment are necessary. A suitable pressure range is from 1 to 10 bar. Subatmospheric pressures are possible, but not preferred. It can be economically advantageous to operate at atmospheric pressure. Other gaseous materials may be present during the conversion of the hydrocarbonaceous feedstock such as steam and/or nitrogen. The process according to the present invention can suitably be carried out in a moving bed of catalyst. Suitably, this is achieved by passing a fluidizing gas through the catalyst bed. The bed of catalyst particles may move upwards or downwards. The bed may be fluidized to the extent that a dispersed catalyst phase is produced when it is desired to operate at very short contact times. When the bed moves upwards as a dispersed phase, for example as is the case when operating in a riser reactor, a process somewhat similar to a fluidized catalytic cracking process is obtained. In this context it should be noted that in conventional fluid catalytic cracking processes the catalyst particles only contain a relatively small content of zeolitic components, since it is generally strongly believed that catalyst particles containing high amounts of zeolitic components do not fulfil attrition requirements. Moreover, in conventional fluid catalytic cracking processes the respective zeolitic components, if applied at all, are customarily incorporated in small amounts into separate matrices. Furthermore, it is contemplated that in processes using respective zeolitic components incorporated in separate matrices an advantageous flexibility in operation is made possible, by the possibility to control the respective amounts of separate zeolite components in the reactor in response to changes in feedstock or in desired product fraction yields. In a further aspect of the present invention it has now been found that in a process according to the invention a catalyst composition may be used comprising a mixture of zeolite II in a matrix as a first component together with an intimate mixture of zeolite I and zeolite II in a matrix as a second component, whereby flexibility of operation is possible. Advantageously, in this aspect of the invention it is also possible to maintain a desired respective amount of zeolite I to zeolite II in the reactor despite any variation due to varying hydrothermal and thermal stability of the two zeolites in the regenerator and to varying attrition resistance of the two zeolites. In the process according to the present invention some coke forms on the catalyst. Therefore it is advantageous to regenerate the catalyst. Preferably, the catalyst is regenerated by subjecting it to a treatment with an oxidizing gas, such as air. A continuous regeneration, similar to the regeneration carried out in a fluidized catalytic cracking process, is especially preferred. In a further aspect of the invention it is found that use of a zeolite I which has equivalent or greater hydrothermal stability than that of zeolite II is particularly advantageous in a process employing regeneration similar to that carried out in a fluidized catalytic cracking process. Suitably, for example, the zeolite I has a ZSM-5 structure. The weight ratio of the catalyst used relative to the hydro¬ carbonaceous feedstock to be converted (catalyst/feedstock weight ratio, kg/kg) may vary widely, for example up to 150 kg catalyst per kg of the hydrocarbonaceous feedstock or even more. Preferably, the catalyst/feedstock weight ratio is from 5 to 150. Suitably, the catalyst/feedstock weight ratio ranges from 7 to 100. If, the process is carried out applying a catalyst/feedstock weight ratio ranging from 20-100 very attractive yields of lower olefins are obtained. The hydrocarbonaceous feedstock which is to be contacted with the zeolitic catalyst in the process of the present invention can vary within a wide boiling range. Examples of suitable feedstocks are relatively light petroleum fractions such as for instance kerosine fractions. Heavier feedstocks may comprise, for example, vacuum distillates, long residues, deasphalted residual oils and atmospheric distillates, for example gas oils and vacuum gas oils. Light fractions such as C_ , hydrocarbons (e.g. LPG) , naphtha or gasoline fractions can suitably be co-processed. Suitably, a hydrogen generating compound such as for instance methanol can be co-processed with the feedstock. Another attractive feedstock comprises a mixture of hydrocarbons obtained in a Fischer-Tropsch hydrocarbon synthesis process. The present invention further relates to a catalyst composition comprising a mixture of a zeolite I and a zeolite II in a matrix material, wherein the zeolite I has a pore diameter of 0.3 to 0.7 nm, zeolite II has a pore diameter greater than 0.7 nm, and the catalyst composition contains at least 25% by weight of zeolitic material. Suitably, the catalyst composition comprises an intimate mixture of the zeolites I and II in a porous matrix material. The above implies that a catalyst particle of the catalyst composition according to present invention contains both zeolites. Preferably, the zeolitic catalyst contains at least 30% by weight of zeolitic material. The zeolitic catalyst can suitably contain up to no less than 50% by weight of zeolitic material. The zeolitic catalyst according to the present invention suitably has a zeolite I/zeolite II weight ratio ranging from 0.1 to 10, preferably from 0.2 to 3. In a further aspect of the invention it has suprisingly been found that in a process of the invention use of a catalyst of the invention having a zeolite I/zeolite II weight ratio ranging from 0.4 to 2.5, more preferably from 0.5 to 2.0, most preferably from 0.55 to 2.0, results in a dramatic reduction in coke formation with respect to use of a catalyst comprising only zeolite II. For example, a catalyst of the invention may have a weight ratio of substantially 1/1. Catalysts having weight ratios in these ranges may be used at higher severity for a constant coke formation than a catalyst comprising only zeolite II allowing a further increase in conversion and gasoline yield. The zeolite I has a pore diameter of 0.3 to 0.7 nm, preferably of 0.5 to 0.7 nm. Suitable and preferred zeolites I, zeolites II and matrix materials include those described hereinbefore. A suitable method for preparing the catalyst composition according to the present invention comprises firstly mixing matrix material with water. The slurry so obtained is then extensively stirred to keep the solids in suspension, and the pH of the slurry is adjusted to the desired value. Subsequently, a physical mixture of the powderous zeolitic components is added to the slurry together with sufficient water to maintain a slurry and to arrive at the desired solids concentration. Thereafter, the slurry is spray-dried and the spray-dried catalyst particles obtained are finally calcined. The invention will now be further described with reference to the following examples. Example 1 Catalyst A according to the invention was prepared as follows: 30 wt % zeolite Y was coblended with 10 wt % ZSM-5, dispersed in matrix material and the resulting composition co-spray-dried. The particles obtained were calcined. Thus, the preparative method for catalyst A was analagous with that of the commercially available catalyst B (ex AKZO) which comprises 30 wt % zeolite Y in matrix. Particles of catalysts A and B were steamed to attain an equilibrium activity. Example 2 The feedstock in this example was a flashed distillate having the following properties: The flashed distillate was treated in a riser reactor in which co-currently a flow of feedstock and catalyst A particles, which comprised an intimate mixture of Y zeolite and ZSM-5 was passed upwards. For comparison purposes, the experiment was repeated with catalyst B which comprised Y zeolite. Experiments were carried out at 2 bar pressure. Further process conditions and the results of the experiments are indicated in the table below, in which the sign "__" indicates olefinic unsaturation. 100.0 100.0 From the above results it will be seen that by operation with catalyst A, the yield of C_- and C,- was significantly increased, whilst the total yield of C„=, C,- and gasoline was also increased with respect to operation with catalyst B.

Claims: C L A I S 1. Process for the preparation of an olefins-containing mixture of hydrocarbons, which process comprises contacting a hydro¬ carbonaceous feedstock with a zeolitic catalyst at a temperature above 480 °C during less than 10 seconds, whereby the zeolitic catalyst comprises a mixture of a zeolite I and a zeolite II in a matrix material, wherein zeolite I has a pore diameter of 0.3 to 0.7 nm and zeolite II has a pore diameter greater than 0.7 nm, and wherein the catalyst contains at least 25% by weight of zeolitic material. 2. Process according to claim 1, wherein the catalyst composition comprises a mixture of zeolite II in a matrix with an intimate mixture of zeolite I and zeolite II in a matrix. 3. Process according to claim 1 or 2, wherein the catalyst composition contains at least 30% by weight of zeolitic material. 4. Process according to any one of claims 1-3, wherein the zeolite I/zeolite II weight ratio ranges from 0.01 to 10. 5. Process according to claim 4, wherein the zeolite I/zeolite II weight ratio ranges from 0.2 to 3. 6. Process according to claim 5, wherein the zeolite I/zeolite II weight ratio ranges from 0.5 to 2.0. 7. Process according to any one of claims 1-6, wherein the feedstock is contacted with the zeolitic catalyst during 0.2 to 6 seconds. 8. Process according to any one of claims 1-7, wherein the temperature is from 500 to 800 °C. 9. Process according to any one of claims 1-8, wherein the pressure is from 1 to 10 bar. 10. Process according to any one of claims 1-9, wherein the catalyst/feedstock weight ratio is from 5 to 150. 11. Process according to any one of claims 1-10, which is carried out in a moving bed of catalyst. 12. A hydrocarbonaceous product, or a fraction thereof, when obtained by the process of any one of claims 1-11. 13. Catalyst composition comprising a mixture of a zeolite I and a zeolite II in a matrix material, wherein the zeolite I has a pore diameter of 0.3 to 0.7 nm, zeolite II has a pore diameter greater than 0.7 nm, and the catalyst composition contains at least 25% by weight of zeolitic material. 14. Catalyst composition according to claim 13, wherein the composition comprises a mixture of zeolite II in a matrix with an intimate mixture of zeolite I and zeolite II in a matrix. 15. Catalyst composition according to claims 13 or 14, wherein the composition contains at least 30% by weight of zeolitic material. 16. Catalyst composition according to any one of claims 13-15, wherein the zeolite I/zeolite II weight ratio ranges from 0.01 to 10. 17. Catalyst composition according to any one of claims 13-16, wherein the zeolite I/zeolite II weight ratio ranges from 0.2 to 3. 18. Catalyst composition according to any one of claims 13-17, wherein the zeolite I/zeolite II weight ratio ranges from 0.5 to 2.0. 19. Catalyst composition according to any one of claims 13-18, wherein zeolite I has a pore diameter of 0.5 to 0.7 nm. 20. Catalyst composition according to any one of claims 13-19, wherein zeolite II comprises a faujasite-type zeolite. 21. Catalyst composition according to claim 20, wherein the zeolite I comprises zeolite Y. 22. Catalyst composition according to any one of claims 13-21, wherein the zeolite II is selected from crystalline (metallo)silicates having a ZSM-5 structure, ferrierite, or mixtures thereof. 23. Catalyst composition according to any one of claims 13-22, wherein the zeolite II is substantially in its hydrogen form. 24. Catalyst composition according to any one of claims 13-23, wherein the matrix material comprises at least one refractory oxide.

Inventors: KHOUW FRANK HSIAN HOK, TERLOUW TEUNIS, VAN ELS AUGUSTINUS CORNELLS CA, WIELERS ANTONIUS FRANZISKUS HE, KHOUW, FRANK, HSIAN, HOK, TERLOUW, TEUNIS, VAN ELS, AUGUSTINUS, CORNELLS, CAROLUS, WIELERS, ANTONIUS, FRANZISKUS, HEINRICH
Applicants: SHELL CANADA LTD, SHELL INT RESEARCH, SHELL CANADA LIMITED, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1992
Main classification: C10G11
IPC codes: B01J29, C10G11, C10G35