PROCESS FOR THE ISOMERIZATION OF ALKYLBENZENES

Abstract: A hydrocarbon conversion process comprises contact­ ing a feed of an alkylbenzene or a mixture of alkylbenzenes un­ der isomerisation conditions in the vapour liquid phase with a catalyst comprising zeolite NU-4. The feed is preferably a xy­ lene or a mixture of xylenes, optionally containing up to 25% by weight ethylbenzene. Compared with a conventional amor­ phous silica-alumina catalyst for xylenes isomerisation, the ze­ olite NUB catalyst produces more para-xylene, destroys a much higher proportion of ethylbenzene (where present) and destroys less of the xylenes.

Description: Hydrocarbon Conversion THIS INVENTION relates to a process for the isomerisation of alkyl benzene hydrocarbons using a catalyst comprising a new zeolite material. The new zeolite material will be referred to hereinafter as "zeolite Nu 4" or simply "Nu4". Zeolite Nu4 and its preparation are described in our co-pending U.K. Patent Application No. 8115407. Zeolite Nu4 has a chemical composition, in terms of mole ratios of oxides, expressed by the formula 0.1 to 7.5 M'O : 0.2 to 5 Y : 100 X02 : O to 50 H20 2 23 wherein M' is a monovalent cation or 1/n of.a cation of valency n, X is silicon or germanium, Y is aluminium, iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese, gallium, or boron, and H20 is water of hydration additional to water notionally present when M' is H, and has an X-ray pattern substantially as set out in Table 1 (as determined by standard technique using copper K7; radiation). Table 1 shows X-ray data for zeolite Nu4 as prepared with reference to the Examples in our co-pending U.K. Patent Application No. 8115407. The X-ray pattern is little affected by the type of cation present or by calcination or hydration. TABLE 1 EMI2.1 <tb> <SEP> Zeolite <SEP> Mu4 <SEP> Zeolite <SEP> Mu4 <SEP> <tb> Example <SEP> 3 <SEP> (as <SEP> made) <SEP> Example <SEP> 4 <SEP> (calcined <SEP> H <SEP> form) <tb> <SEP> dA <SEP> 1001/10 <SEP> dA <SEP> 1001/10 <SEP> <tb> 11.3 <SEP> 16 <SEP> 11.07 <SEP> 33 <tb> 11.1 <SEP> 20 <SEP> 10,07 <SEP> 36 <tb> 10.08 <SEP> 15 <SEP> 9,96 <SEP> 10 <tb> <SEP> 9.90 <SEP> 8 <SEP> 9.79 <SEP> 10 <tb> <SEP> 9.77 <SEP> 6 <SEP> 9.28 <SEP> 1 <tb> <SEP> 9.05 <SEP> 1 <SEP> 9.02 <SEP> 1.5 <tb> <SEP> 7.50 <SEP> 2 <SEP> 8.08 <SEP> 1 <tb> <SEP> 7.09 <SEP> 1 <SEP> 7.45 <SEP> 4 <tb> <SEP> 6.78 <SEP> 2 <SEP> 7.09 <SEP> 2 <tb> <SEP> 6.44 <SEP> 5 <SEP> 6.72 <SEP> 4 <tb> <SEP> 6.07 <SEP> 4 <SEP> 6.38 <SEP> 8 <tb> <SEP> 6.05 <SEP> 5 <SEP> 6.08 <SEP> 5 <tb> <SEP> 5.97 <SEP> 1 <SEP> 6.02 <SEP> 7 <tb> 5.75 <SEP> 8 <SEP> 5.99 <SEP> 7 <tb> 5.65 <SEP> 6 <SEP> 5.73 <SEP> 9 <tb> 5.63 <SEP> 2 <SEP> 5.57 <SEP> 8 <tb> 5.41 <SEP> 2 <SEP> 5.38 <SEP> 2 <tb> 5.19 <SEP> 2 <SEP> 5.15 <SEP> 4 <tb> 5.07 <SEP> 2 <SEP> <SEP> 5.04 <SEP> 3 <tb> <SEP> 5.01 <SEP> 4 <SEP> 5.005 <SEP> 5 <tb> <SEP> 4.915 <SEP> 1 <SEP> 4.899 <SEP> 1 <tb> 4.629 <SEP> 9 <SEP> 4.725 <SEP> 1 <tb> 4.558 <SEP> 1 <SEP> 4.610 <SEP> 9 <tb> <SEP> 4.495 <SEP> 2 <SEP> 4.560 <SEP> 2 <tb> 4.475 <SEP> 2 <SEP> 4.490 <SEP> 1 <tb> <SEP> 4.386 <SEP> 13 <SEP> 4.470 <SEP> 2 <tb> <SEP> 4.291 <SEP> 10 <SEP> 4.330 <SEP> 14 <tb> <SEP> 4.124 <SEP> 13 <SEP> 4.280 <SEP> 13 <tb> <SEP> 4.104 <SEP> 4.103 <SEP> 3 <tb> <SEP> 4.039 <SEP> 4.022 <SEP> 7 <tb> <SEP> 3.950 <SEP> 1 <SEP> 3.950 <SEP> 2 <tb> Table 1 (contd) EMI3.1 <tb> <SEP> Zeolite <SEP> Nu4 <SEP> Zeolite <SEP> Nu4 <tb> Example <SEP> 3 <SEP> (as <SEP> made) <SEP> Example <SEP> 4 <SEP> (calcined <SEP> H <SEP> form) <tb> <SEP> dA <SEP> 1001/10 <SEP> dA <SEP> 1001/10 <tb> <SEP> 3.880 <SEP> 100 <SEP> 3.869 <SEP> 100 <tb> 3.860 <SEP> 69 <SEP> 3.836 <SEP> 73 <tb> 3.743 <SEP> 51 <SEP> 3.764 <SEP> 35 <tb> 3.730 <SEP> 50 <SEP> 3.735 <SEP> 54 <tb> 3.678 <SEP> - <SEP> <SEP> 27 <SEP> 3.662 <SEP> 29 <tb> 3.649 <SEP> 22 <SEP> 3.604 <SEP> 4 <tb> 3.629 <SEP> 5 <SEP> 3.500 <SEP> 5 <tb> 3.466 <SEP> 12 <SEP> 3.469 <SEP> 10 <tb> 3.364 <SEP> 6 <SEP> 3.368 <SEP> 7 <tb> 3.332 <SEP> 9 <SEP> 3.342 <SEP> 10 <tb> 3.329 <SEP> 4 <SEP> 3.265 <SEP> 3 <tb> 3.273 <SEP> 4 <SEP> 3.260 <SEP> 12 <tb> 3.267 <SEP> 4 <tb> 3.260 <SEP> 4 <tb> Within the above definition of chemical composition, the number of moles of Y203 is typically in the range 0.2 to 5 and zeolite Nu4 appears to be most readily formed in a state of high purity when the number of moles of Y203 is in the range 0.5 to 2. This definition includes both freshly prepared zeolite Nu4 ("freshly prepared" means the product of synthesis and washing, with optional drying, as described in our co-pending U.K. Patent Application No. 8115407) and also forms of it resulting from dehydration, and/or calcination, and/or ion exchange. In freshly prepared zeolite Nu4, M' may include an alkali metal cation especially sodium, and/or ammonium, and usually orwhen prepared from nitrogen compounds, includes nitrogen-containing organic fro cations as described below or cationic degradation products thereof, or precursors thereof. These nitrogen containing cations are hereinafter referred to as Q. The alkali metal cation comprising M' may also be potassium or rubidium but the Applicants have found that use of these two cations during synthesis of zeolite NU-4 may also result in the co-production of zeolite NU-10 as an impurity (Zeolite NU-10 is described and claimed in our co-pending United Kingdom Patent Application No. 81154102. The freshly prepared zeolite Nu4 may also contain nitrogencontaining compounds typically in the range 0.4 to 6 moles per mole of X02. Since Nu4 is a zeolite, the nitrogen containing base must be physically trapped within the crystal lattice. It can be removed by thermal or oxidative degradation or by displacement by suitable small molecules. This physically trapped basic material does not constitute part of the composition for the purposes of the definition. Thus a zeolite Nu-4 as made typically has the following molar composition: 0.1 to 7.5 M210 : 0.4 to 6 Q : 0.2 to 5 Y203 : 100 X02 : O to 50 H20 wherein M' is an alkali metal or ammonium or hydrogen. The H20 content of freshly prepared zeolite Nu4 depends on the conditions in which it has been dried after synthesis. In calcined forms of zeolite Nu4, M' may be alkali metal but includes less or no nitrogen-containing organic compounds, since these are burnt out in the presence of air, leaving hydrogen as the other balancing cation, or otherwise displaced prior to calcination. Among the ion-exchanged forms of zeolite Nu4 the ammonium (No4+) is of importance since it can be readily converted to the hydrogen form by calcination. The hydrogen form can also be prepared directly by exchange with an acid. The hydrogen-free and forms containing metals introduced by ion exchange are described further below. We believe that zeolite Nu4 is a new member of the ZSMS/11 series of zeolites, which has the lowest symmetry possible for members of this series. ZSM1l has the highest i.e. has tetragonal symmetry. ZSM5 usually exhibits orthorhombic symmetry, but recently (E L Wu et al J Phys. Chem. 83, 2777 (1979))it has been claimed that ZSM5, under special circumstances, can exhibit pseudo monoclinic symmetry. Specific treatments e.g. NH4 exchange, calcination, sorption, can cause displacive transformation from orthorhombic to pseudo monoclinic symmetry. These transformations are completely reversible and in ZSM5 depend only upon the ions or sorbate present within the ZSMS lattice. We have found that zeolite Nu4 as made, or in all its ionexchanged, calcined, hydrated, dehydrated or sorbing forms, always exhibits true monoclinic symmetry. This is best demonstrated by reference to Nature 275, 120 (1978), where it is noted that the major clue to differences in structure, between the closely related zeolites ZSMS and ZSMll, came from differences in X-ray diffraction data. In the diffraction data for ZSMS (orthorhombic) there is a significant splitting of certain ZSMll (tetragonal) type peaks into doublets and there are variations in peak heights. This behaviour confirms that ZSMS has a lower order of symmetry than ZSMll, but is nevertheless closely related. In going from tetragonal ZSMS to pseudo-monoclinic ZSMS there is further marginal peak splitting. However in the case of zeolite Nu4 there is very substantial splitting of peaks as compared with tetragonal or even pseudo monoclinic ZSMS. This splitting includes many new doublets and even triplets, and also marked variations in line intensities. According to the present invention a hydrocarbon conversion process comprises contacting a feed of an alkylbenzene or a mixture of alkylbenzenes under isomerisation conditions in the vapour or liquid phase with a catalyst comprising zeolite Nu4. The catalyst used in the process of this invention may be zeolite Nu4 per se but in a preferred embodiment of the process zeolite Nu4 is used in the form of a physical mixture with a suitable diluent and/or binder, for example alumina, silica or a clay. Alumina is particularly preferred as a diluent, the amount of alumina present in the catalyst being preferably in the range 5 to 95 by weight based on total catalyst weight. In the vapour phase, suitable isomerisation conditions for the process of this invention include a temperature in the range 100 to 6000C, preferably 200 to 4500C and a pressure in the range 0.5 to 50, preferably 1 to 5 atmospheres absolute. In the liquid phase embodiment of the process of this invention, suitable isomerisation conditions include a temperature in the range 0 to 350 C, a pressure in the range 1 to 200, preferably 5 to 7, atmospheres absolute and, in a flow system, a space velocity in the range 0.1 to 100, preferably 0.5 to 30, wZw hour, the higher flow rates being used at the higher temperatures. Optionally a diluent is present, suitably one or more of those having a critical temperature higher than the isomerisation temperature being used and including toluene, trimethylbenzene, naphthenes and paraffins. Preferably, the diluent if present, amounts to l to 90% of the feed to the isomerisation reaction. In the above mentioned forms of the process of this invention the catalyst preferably contains no hydrogenationfdehydrogenation component. Optionally the isomerisation reaction is conducted in the presence of hydrogen. A suitable mole ratio of hydrogen to alkylbenzene lies in the range 1:1 to 30:1. If hydrogen is used, it is preferred that the catalyst should comprise a metal of Group VIII of the Periodic Table together with the zeolite. Preferably the metal of Group VIII is platinum or nickel. The amount of metal used preferably lies in the range 0.1 to 2% by weight of metal based on the total weight of catalyst. If desired, the catalyst may contain one or more additional metals, for example rhenium, suitably in the range 0.1 to 2% by weight based on the total weight of catalyst. Preferably the alkylbenzene is a xylene, for example m-xylene for conversion to p-xylene, or a mixture of xylenes, possibly with ethylbenzene. The amount of ethylbenzene present will depend to some extent on the source of the xylene mixture but will usually lie in the range 0 to 25% by weight of the feedstock. However, we believe that the process of this invention is very suitable for conversion to para-xylene of at least some of the ethylbenzene in feedstocks containing relatively large amounts of ethylbenzene, say in the range 6 to 25% by weight of the feedstock. The invention is illustrated by the following Examples. EXAMPLE 1 A sample of zeolite Nu4 prepared as described in Example 2 of our co-pending U.K. Patent Application No. 8115407 was formed into aggregates -having diameters in the size range of 425 to lOOOymm. The sample was charged to a glass reactor and heated in a stream of air at 500 C for 16 hours. It was then cooled in a nitrogen stream to 4000C. A feedstock of the following composition (all % by weight) was then passed over the sample at atmospheric pressure and 4000C. Benzene 0.2% Toluene 1.96% Ethylbenzene 8.78% Paraxylene 8.24% Metaxylene 50.07% Orthoxylene 25.80% Cg+ aromatics 3.72% Results are given in Table 2. EXAMPLE 2 Example 1 was repeated using a sample of zeolite Nu4 prepared according to Example 4 of our co-pending U.K. Patent Application No. 8115407, and formed in aggregates having diameters in the size range of 425 to l000 ffi m. Results are given in Table 2. EXAMPLE 3 Example 2 was repeated but in this case the sample of zeolite Nu4 was mixed with gamma-alumina powder in the weight ratio (zeolite alumina) of 1:4 and again formed into aggregates having diameters in the size range of 425 to 1000rm, Results are given in Table 2. COMPARATIVE EXAMPLES 1 AND 2 Example 1 was repeated but using two other catalysts for comparative purposes. In comparative Example 1 a sample of zeolite ZSM-5 was used which had been prepared according to the method described in German OLS 2,548,695 and formed into aggregates having diameters in the size range 425 to 1000cam. In comparative Example 2 a sample of amorphous silicaalumina catalyst in the form of 3 to 5mm beads, containing 10% alumina, was used. In this case only, the reaction temperature was 4500C. Results of all three Examples and the two Comparative Examples are-given in Table 2. TABLE 2 EMI8.1 <tb> <SEP> EXAMPLE <SEP> EXAMPLE <SEP> EXAMPLE <SEP> COMPARATIVE <SEP> EXAMPLES <tb> <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 1 <SEP> 2 <tb> Weight <SEP> Hourly <SEP> Space <tb> Velocity <SEP> 19 <SEP> 82 <SEP> 30 <SEP> 83 <SEP> 1 <tb> Para-xylene <SEP> content <SEP> 17.9 <SEP> 17.8 <SEP> 17.9 <SEP> 17.9 <SEP> 17.2 <tb> of <SEP> product <SEP> (%) <tb> Xylenes <SEP> lost <SEP> (%) <SEP> 2.1 <SEP> 4.35 <SEP> 1.7 <SEP> 0.6 <SEP> 5.1 <tb> Ethylbenzene <SEP> 49.1 <SEP> 46.0 <SEP> 44.1 <SEP> 18.0 <SEP> 12.8 <tb> lost <SEP> (%) <tb> The results illustrate that 1. compared with amorphous silica-alumina, the zeolite Nu4 catalyst produces more paraxylene, destroys a much higher proportion of ethylbenzene and destroys less xylenes. 2. compared with zeolite ZSM5, for the same paraxylene production zeolite Nu4 destroys rather more xylenes and much more ethyl benzene. 3. dilution of zeolite Nu4 with alumina decreases the extent of xylenes loss while still maintaining the ethylbenzene destruction. The greater ability of zeolite Nu4 to destroy ethylbenzene is likely to be a useful asset in the future. In existing xylenes plants a feedstock which is comparatively low in ethylbenzene is usually'used and destruction of ethylbenzene is fairly readily accomplished. However, in the future it is likely that xylene manufacturers will have to turn to feedtsocks containing much higher amounts of ethylbenzene as the low-ethylbenzene feedstocks are expected to become much less readily available. In those circumstances, the ability of a catalyst such as zeolite Nu4 to not only effect isomerisation of the other xylenes to valuable paraxylene but also destroy the greater amounts of ethylbenzene in the feedstock will be a considerable asset.

Claims: Claims 1. A hydrocarbon conversion process which comprises contacting a feed of an alkylbenzene or a mixture of alkylbenzenes under isomerisation conditions in the vapour or liquid phase with a catalyst comprising zeolite Nu4. 2. A process as claimed in claim 1 in which the catalyst comprises zeolite NU-4 in the form of a physical mixture with a diluent and/or a binder material. 3. A process as claimed in claim 2 in which the diluent is alumina which is present in an amount of 5 to 95% by weight based on total catalyst weight. 4. A process as claimed in any one of the preceding claims in which the process is carried out in the vapour phase at a temperature in the range 100 to 6000C and at a pressure in the range 0.5 to 50 atmospheres absolute. 5. A process as claimed in any one of claims 1 to 3 in which the process is carried out in the liquid phase at a temperature in the range 0 to 350 0C and at a pressure in the range 1 to 200 atmospheres absolute. 6. A process as claimed in any one of the preceding claims in which the process is carried out in the presence of hydrogen, the hydrogen being present in an amount such that the mole ratio of hydrogen to alkylbenzene is in the range 1:1 to 30:1. 7. A process as claimed in claim 6 in which the catalyst comprises a metal of Group VIII of the Periodic Table together with zeolite NU-4. 8. A process as claimed in claim 7 in which the Group VIII metal is platinum or nickel which is present in an amount of 0.1 to 2% by weight based on the total weight of catalyst. 9. A process as claimed in any one of the preceding claims in which the alkylbenzene is a xylene or a mixture of xylenes containing from 0 to 25% by weight of ethylbenzene.

Inventors: LAKE, IVAN JAMES SAMUEL, WHITTAM, THOMAS VINCENT
Applicants: IMPERIAL CHEMICAL INDUSTRIES PLC
Application year: 1982
Main classification: C07C15
IPC codes: B01J29, C07C15, C07B61, C07C1, C07C5, C07C67