NZ234416A

NZ234416A - Reforming naphtha with boron-containing large-pore zeolites

Info

Publication number: NZ234416A
Application number: NZ234416A
Authority: NZ
Inventors: Stacey I Zones; Dennis L Holtermann; Andrew Rainis
Original assignee: Chevron Res & Tech
Priority date: 1990-01-26
Filing date: 1990-07-09
Publication date: 1992-05-26
Also published as: EP0465606A1; EP0465606A4; AU5965390A; JPH04504439A; KR920701398A; CA2049928A1; WO1991011501A1

Description

<div id="description" class="application article clearfix"> New Zealand Paient Spedficaiion for Paient Number £34416 234416 Compteta Sp&clilcsilof Class: (5)...C.10..■/]>., P\iD5iC9t!£>n P.O. JoUKiaf. li EALAND PATENTS ACT, 1953 (|Q ^fiNTfOFftOE No.: Date: COMPLETE SPECIFICATION "REFORMING NAPHTHA WITH BORON-CONTAINING LARGE-PORE ZEOLITES" spy We CHEVRON RESEARCH AND TECHNOLOGY COMPANY, a corporation duly organised under the laws of the State of Delaware, USA, of 100 West Tenth Street, Wilmington, Delaware, USA, and having a place of business at 555 Market Street, San Francisco, CA, USA hereby declare the invention for which 5T"/ we pray that a patent may be granted to -pas/us, and the method by which it is to be performed, to be particularly described in and by the following statement; - - 1 - (followed by page la) 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2 3 4 4 1 6 REFORMING NAPHTHA WITH BORON-CONTAINING LARGE-PORE ZEOLITES BACKGROUND OF THE INVENTION Catalytic reforming is a process for treating naphtha fractions of petroleum distillates to improve their octane rating by producing aromatic components and isomerizing paraffins from components present in naphtha feedstocks. Included among the hydrocarbon reactions occurring in reforming processes are: dehydrogenation of naphthenes to aromatics, dehydrocyclization of paraffins to aromatics, and hydrocracking of paraffins to lighter gases with a lower boiling point than gasoline. Hydrocracking reactions which produce light paraffin gases are not desirable as they reduce the yield of products in the gasoline range. Natural and synthetic zeolitic crystalline aluminosilicates and borosilicates are useful as catalysts. The use of ZSM-type catalysts and processes are described in U.S. Patent Nos. 3,546,102, 3,679,575, 4,018,711 and 3,574,092. Zeolite L is also used in reforming processes as described in U.S. Patent Nos. 4,104,320, 4,447,316, 4,347,394 and 4, 434 , 311 . Borosilicate zeolites are especially useful in catalytic reforming. Methods for preparing high silica content zeolites that contain framework boron are described in U.S. Patent No. 4,269,813. The use of intermediate pore borosilicate zeolites for catalytic reforming is described in European Patent Application No. 188,913. In this application, ZSM-5, -lea 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234416 ZSM-l1, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and zeolite beta have been identified as intermediate pore borosilicate zeolites. A method for controlling catalytic activity of large-pore According to the present invention, a process is provided for catalytic reforming. The process comprises contacting a hydrocarbon feedstream under catalytic reforming conditions with a composition comprising large-pore borosilicate zeolites having a pore size between 6 and 8 angstroms. Preferably, the large-pore borosilicate zeolites are boron beta zeolite, (B)SSZ-24, SSZ-31 and SSZ-33. Boron beta zeolite is described in commonly assigned New Zealand Patent Application No. 234,405, and entitled "Low-Aluminum Boron Beta Zeolite", the disclosure of which is incorporated herein by reference. Patent Application No. 234,403, and entitled "Zeolite (B)SSZ-24", the disclosure of which is incorporated herein by reference. SSZ-33 is described in commonly assigned New Zealand Patent Application No. 233,714, and entitled "Zeolite SSZ-33", the disclosure of which is incorporated herein by reference. boron-containing zeolites is described in European Patent Application No. 234,759. SUMMARY OF INVENTION (B)SSZ-24 is described in commonly assigned New_Zealand -2- >344 6 SSZ-31 is described in commonly assigned co-pending ®2<T application U.S. Serial No. 471158 (Docket No. B-3986 ), filed concurrently herewith, and entitled "New Zeolite 04 05 06 07 08 09 10 23 24 25 26 28 29 32 33 SSZ-31", the disclosure of which is incorporated herein by refe rence. According to a preferred embodiment, the large-pore borosilicate zeolites may be used in a multi-stage catalytic reforming process. These zeolites may be located in one or more of the reactors, with conventional platinum and rhenium H catalysts located in the remaining reactors. 12 1 3 The reforming process may be accomplished by using fixed beds, fluid beds or moving beds for contacting the hydrocarbon feedstream with the catalysts. 16 n Among other factors, the present invention is based on our finding that large-pore borosilicates including boron beta zeolite [(B)Beta], SSZ-33, (B)SSZ-24 and SSZ-31 have 2® unexpectedly outstanding reforming properties. These 21 include high sulfur tolerance, high catalyst stability, and 22 high catalyst activity. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to reforming processes 27 employing large-pore borosilicate zeolites. A large-pore zeolite is defined herein as a zeolite having a pore size between 6 and 8 angstroms. A method of determining this 30 pore size is described in Journal of Catalysis (1986); 31 Vol. 99, p. 335 (D. S. Santilli). A large-pore zeolite may be identified by using the pore probe technique described in Journal of Catalysis (1986); Vol. 99, p. 335 (D. ,S. Santilli). This method allows measurement of the -3- ;/'V v 5APR 1992 •' / -?V? p | 23 4 4 1 01 steady-state concentrations of compounds within the pores of 02 materials. 2,2-dimethylbutane (22DMB) enters the large 22 23 24 25 26 [U 27 28 29 30 31 32 33 34 pores and the concentration in the pores is measured using this technique. According to preferred embodiments of our invention, SSZ-33, (B)SSZ-24, SSZ-31 and low-aluminum boron beta zeolite [(B)beta] are large-pore borosilicate zeolites with high catalyst activity in the reforming process. 03 04 05 06 07 08 09 10 11 SSZ-33 is defined as a zeolite having a mole ratio of an 12 oxide selected from silicon, germanium oxide and mixtures 13 thereof to an oxide selected from boron oxide or mixtures of 1^ boron oxide with aluminum oxide, gallium oxide or iron 15 oxide, greater than about 20:1 and having the X-ray 16 diffraction lines of Table 1. The X-ray diffraction lines 17 of Table 1 correspond to the calcined SSZ-33. 18 19 Table 1 20 21 2 e d/n 100 x I/I 0 7.86 11.25 90 20.48 4.336 100 21.47 4.139 40 22.03 4.035 90 23.18 3.837 64 26.83 3.323 40 (B)SSZ-24 is defined as a zeolite having a mole ratio of an oxide selected from silicon oxide, germanium oxide, and mixtures thereof to an oxide selected from boron oxide or mixtures of boron oxide with aluminum oxide, gallium oxide, -4- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2 3 4 4 and iron oxide, between 20:1 and 100:1 and having the X-ray diffraction lines of Table 2. The X-ray diffraction lines of Table 2 correspond to the calcined (B)SSZ-24. Table 2 2 e d/n 100 x I/I 7.50 11.79 100 13.00 6.81 16 15.03 5.894 8 19.93 4.455 35 21.42 4.148 48 22.67 3.922 60 25.15 3.541 3 26.20 3.401 22 29.38 3.040 12 30.43 2.947 12 Boron beta zeolite is a zeolite having a mole ratio of an oxide selected from silicon oxide, germanium oxide, and mixtures thereof to an oxide selected from boron oxide, or mixtures of boron oxide with aluminum oxide, gallium oxide or iron oxide, greater than 10:1 and wherein the amount of aluminum is less than 0.10% by weight and having the X-ray diffraction lines of Table 3. The X-ray diffraction lines of Table 3 correspond to the calcined boron beta zeolite. -5- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 Table 3 2 0 d/n 100 x I/I ' o Shape 7.7 11.5 85 Broad 13.58 6.52 9 14.87 5.96 12 Broad 18.50 4.80 3 Very Broad 21.83 4.07 15 22.87 3.89 100 Broad 27.38 3.26 10 29.30 3.05 6 Broad 30.08 2.97 8 SSZ-31 is defined as a zeolite having a mole ratio of an oxide selected from silicon oxide, germanium oxide, and mixtures thereof to an oxide selected from aluminum oxide, gallium oxide, iron oxide, and mixtures thereof greater than about 50:1, and having the X-ray diffraction lines of Table 4. The X-ray diffraction lines of Table 4 correspond to the calcined SSZ-31. Table 4 2 9 d/n 100 x I/I 0 Shape 6.08 14.54 9 7.35 12.03 9 8.00 11.05 7 Broad 18.48 4.80 11 20.35 4. 36 9 Broad 21.11 4.21 100 22.24 4.00 56 24 .71 3.60 21 30.88 2.90 7 -6- 23 4 4 ' °1 The large-pore borosilicat.es can be used as reforming 02 catalysts to convert light straight run naphthas and similar mixtures to highly aromatic mixtures. Thus, normal and slightly branched chained hydrocarbons, preferably having a boiling range above about 40°C and less than about 250°C, can be converted to products having a substantial aromatics content by contacting the hydrocarbon feed with the zeolite at a temperature in the range of from about 400°C to 600°C, at pressures ranging from atmospheric to 20 atmospheres, LHSV ranging from 0.1 to 15, and a recycle hydrogen to hydrocarbon ratio of about 1 to 10. 12 13 The reforming catalyst preferably contains a Group VIII 14 metal compound to have sufficient activity for commercial | 15 use. By Group VIII metal compound as used herein is meant 1^ the metal itself or a compound thereof. The Group VIII 1^ noble metals and their compounds, platinum, palladium, and 1® iridium, or combinations thereof can be used. The most 19 preferred metal is platinum. The amount of Group VIII metal 03 04 05 06 07 08 09 10 20 present in the conversion catalyst should be within the 21 normal range of use in reforming catalysts, from about 0.05 22 to 2.0 wt. percent, preferably 0.2 to 0.8 wt. percent. In 23 addition, the catalyst can also contain a second Group VII 24 metal. Especially preferred is rhenium. 25 26 The zeolite/Group VIII metal catalyst can be used with or ^ 27 without a binder or matrix. The preferred inorganic matrix, 28 where one is used, is a silica-based binder such as 29 Cab-O-Sil or Ludox. Other matrices such as alumina, 30 magnesia and titania can be used. The preferred inorganic 31 matrix is nonacidic. 32 33 34 r> 2 3 4 4 16 01 02 03 04 05 06 07 08 09 10 It is critical to the selective production of aromatics in useful quantities that the conversion catalyst be substantially free of acidity, for example, by exchanging the sites in the zeolite with metal ions, e.g., Group I and Group II ions. The zeolite is usually prepared from mixtures containing alkali metal hydroxides and thus, have alkali metal contents of about 1-2 wt. %. These high levels of alkali metal, usually sodium or potassium, are unacceptable for most other catalytic applications because they greatly deactivate the catalyst for cracking reactions H by reducing catalyst acidity. Therefore, the alkali metal 12 is removed to low levels by ion exchange with hydrogen or 13 ammonium ions. By alkali metals as used herein is meant 1^ ionic alkali metals or their basic compounds. Surprisingly, I5 unless the zeolite itself is substantially free of acidity, 1® the alkali metal is required in the present process to 17 reduce acidity and improve aromatics production. Alkali 1® metals are incorporated by impregnation or ion exchange 19 using nitrate, chloride or carbonate salts. 20 21 The amount of alkali metal necessary to render the zeolites ^ 22 substantially free of acidity can be calculated using 23 standard techniques based on the aluminum, gallium or iron 24 content of the zeolites. If a zeolite free of alkali metal is the starting material, alkali metal ions can be ion exchanged into the zeolite to substantially eliminate the acidity of the zeolite. An alkali metal content of about 2® 100%, or greater, of the acid sites calculated on a molar 29 basis is sufficient. 30 31 where the metal ion content is less than 100% of the acid 32 sites on a molar basis, the test described in U.S. Patent 33 No. 4,347,394, which patent is incorporated totally herein 34 25 26 J 27 -8- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 23^4 16 by reference, can be used to determine if the zeolite is substantially free of acidity. The preferred alkali metals are sodium, potassium, and cesium, as well as other Groups IA and IIA metals. The zeolites can be substantially free of acidity only at very high silica:alumina mole ratios; by "zeolite consisting essentially of silica" is meant a zeolite which is substantially free of acidity without base poisoning. A low sulfur feed is preferred in the reforming process; but due to the sulfur tolerance of these catalysts, feed desulfurization does not have to be as complete as with conventional reforming catalysts. The feed should contain less than 10 parts per million sulfur. In the case of a feed which is not low enough in sulfur, acceptable levels can be reached by hydrogenating the feed with a hydrogenating catalyst which is resistant to sulfur poisoning. An example of a suitable catalyst for this hydrodesulfurization process is an alumina-containing support and a minor catalytic proportion of molybdenum oxide, cobalt oxide and/or nickel oxide. A platinum on alumina hydrogenating catalyst can also work. In which case, a sulfur sorber is preferably placed downstream of the hydrogenating catalyst, but upstream of the present reforming catalyst. Examples of sulfur sorbers are alkali or alkaline earth metals on porous refractory inorganic oxides, zinc, etc. Hydrodesulfurization is typically conducted at 315-455°C, at 200-2000 psig, and at a LHSV of 1-5. -9- ) 01 02 03 04 05 06 07 00 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 1 6 It. is preferable to limit the nitrogen level and the water content of the feed. Catalysts and processes which are suitable for these purposes are known to those skilled in the art. After a period of operation, the catalyst can become deactivated by coke. Coke can be removed by contacting the catalyst with an oxygen-containing gas at an elevated temperature. If the Group VIII metal(s) have agglomerated, then it can be redispersed by contacting the catalyst with a chlorine gas under conditions effective to redisperse the metal(s). The method of regenerating the catalyst may depend on whether there is a fixed bed, moving bed, or fluidized bed operation. Regeneration methods and conditions are well known in the art. The reforming catalysts preferably contain a Group VIII metal compound to have sufficient activity for commercial use. By Group VIII metal compound as used herein is meant the metal itself or a compound thereof. The Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium and tin may also be used in conjunction with the noble metal. The most preferred metal is platinum. The amount of Group VIII metal present in the conversion catalyst should be within the normal range of use in reforming catalysts, from about 0.05-2.0 wt. %. , Example 1 Preparation of Platinum-(B)SSZ-24 The borosilicate version of (B)SSZ-2'4 was prepared for use as a reforming catalyst. The zeolite powder was impregnated -10- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 23 4 4 with Pt(NH^)^"2NO3 to give 0.8 wt. % Pt. The material was calcined up to 550°F in air and maintained at this temperature for three hours. The powder was pelletized on a Carver press at 1000 psi and broken and meshed to 24-40. Example 2 Reforming Test Results (B)SSZ—24 from Example 1 was tested as a reforming catalyst. The conditions for the reforming test were as follows. The catalyst was prereduced for 1 hour in flowing hydrogen at 950°F and atmospheric pressure. Test conditions were: Total Pressure = 200 psig E^/HC Molar Ratio = 6.4 WHSV = 6 hr-1 The catalyst was initially tested at 800°F and then at 900°F. The feed was an iC^ mixture supplied by Philips Petroleum Company. The catalyst from Example 1 was tested with these results. Feed Products Temperature, °F 800°F 900°F Conversion % 0 79.6 100 Toluene, wt. % 0.5 22.1 21.9 Cg-Cg Octane, RON 63.7 86.8 105.2 C5+ Yield, wt. % 100 54.9 35.4 Aromatization Selectivity, % 32.1 30.2 Toluene in the Cg+ Aromatics % 86.6 72.7 -11- 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2 3 4 4 As shown by the complete conversion, this catalyst is capable of converting all types of feedstock molecules. Example 3 Preparation and Testing of a Neutralized Platinum-Aluminum-Boron SSZ-24 Aluminum was substituted into the borosilicate version of (B)SSZ-24 by refluxing the zeolite with an equal mass of Al (NOg ) 2* 9^0 overnight. Prior to use, the aluminum nitrate was dissolved in 1^0 at a ratio of 50:1. The product contained acidity due to the aluminum incorporation, and this would lead to unacceptable cracking losses. Two back ion exchanges with KNOg were performed and the catalyst was calcined to 1000°F. Next, a reforming catalyst was prepared as in Example 1. It was tested as in Example 2. Feed Products Temperature, °F 800 900 Conversion % 0 53.0 95.1 Toluene, wt. % 0.5 22.6 26.6 C5-Cg Octane, RON 63.7 78.1 99.6 C5+ Yield, wt. % 100 81.5 46.2 Aromatization Selectivity, % ■ 47.1 35.7 Toluene in the Cg+ Aromatics % 90.6 78.1 By comparison with Example 2, the incorporation of aluminum, accompanied by its neutralization, gives a less active, but more selective catalyst. -12- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 1 Example 4 Preparation and Testing of a Platinum-Boron-Beta Catalyst The borosilicate version of boron beta was impregnated with Pt(NH^)^"2N0g to give 0.8 wt. % Pt. The material was calcined up to 550°F in air and maintained at this temperature for three hours. The powder was pelletized on a Carver press at 1000 psi and broken and meshed to 24-40. The catalyst was tested as shown in Example 2 with the exception that operation at both 200 and 50 psig were explored. Pressure, psig 200 50 200 Temperature, °F 800 800 900 Conversion % CO CO 8 77 .0 100 Toluene, wt. % 19. 1 39 .3 16. 9 Cg-Cg Octane, RON 00 vo 5 90 .6 104. 3 Cg+ Yield, wt. % 46. 9 77 .4 30. 2 Aromatization Selectivity, % 25. 4 54 .5 25. 3 Toluene in the Cg+ Aromatics % CO 9 93 .7 67. 8 The catalyst is quite stable and the values are averaged over at least 20 hours of run time. , Example 5 Preparation and Testing of a Platinum-Cobalt-Boron-Beta Catalyst Cobalt was incorporated into the boron beta as described in Example 3 with Co(NO^)^ '6H20 as the cobalt source replacing -13- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2344 16 Al (NO^ ) ^ ' 9^0 as the aluminum source in Example 3. The catalyst was calcined to 1000°F, and a Platinum reforming catalyst was prepared as described in Example 1. It was tested as described in Example 2 except the WHSV was 12 and operation at both 200 and 100 psig was evaluated. Pressure, psig 200 100 Temperature, °F 800 800 Conversion % 83.3 86.0 Toluene, wt. % 18.8 27.3 C5~C8 0ctane' R0N 85.3 90.3 Cg+ Yield, wt. % 59.8 63.7 Aromatization Selectivity, % 27 37 Toluene in the C^+ Aromatics % 83.3 85.9 By comparison with Example 4, the incorporating of cobalt gives a more active catalyst. The catalyst has good stability at 800°F. Example 6 Preparation of Pt-SSZ-33 SSZ-33 was prepared for use as a reforming catalyst. The zeolite powder was impregnated with Pt(NH^)^'2NOj to give 0.8 wt. % Pt. The material was calcined up to 550°°F in air and maintained at this temperature for three hours. The powder was pelletized on a Carver press at 1000 psi and broken and screened to 24-40 mesh. -14- * 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 1 Example 7 Preparation of Pt-Zinc-SSZ-33 Zinc was incorporated into the novel large-pore borosilicate SSZ-33 by refluxing ZnfAc^'^O as described in Example 3. The product was washed, dried, and calcined to 1000°F, and then impregnated with Pt(NH^)^to give 0.8 wt.% Pt. The material was calcined up to 550°F in air and maintained at this temperature for three hours. The powder was pelletized on a Carver press at 1000 psig, broken, and meshed to 24-40. It was tested as described in Example 2. Results are as follows: Pressure, psig 200 Temperature, °F 900 Conversion % 71.1 Toluene, wt. % 28 C5-C8 0ctane' R0N 8!) C^+ Yield, wt. % 74.2 Aromatization Selectivity, % 44.5 Toluene in the Cg+ Aromatics % 88.5 -15- 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234 4 Example 8 Testing of Pt-SSZ-33 and Pt-Zinc-SSZ-33 The catalysts of Examples 6 and 7 were tested with a partially reformed naphtha at: Total Pressure = 50 psig H-/HC Molar Ratio = 3 -1 LHSV = 2 hr These conditions simulate use of the catalyst in the last reactor of a multi-stage reforming process. An analysis of the feed and products is shown below. Feed Products Molecular Sieve Pt-SSZ-33 Pt-Zn-SSZ-33 Temperature, °F 780 860 Composition, wt. % C4- 0 13.4 9.4 C5's Total 0 8.3 7.0 Cg Paraffins 8.7 8.3 7.7 Cg Naphthenes 1.0 0.9 0.9 Benzene 1.6 3.5 2.6 -16- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 2 3 4 4 Feed C-j Paraffins 8.6 Naphthenes 0.2 Toluene 8.8 Cg Paraffins 5.8 Cg Naphthenes 0.1 Cg Aromatics 21.1 Cg Paraffins 2.1 Cg+ Aromatics 32.3 Octane, RON 94.6 C5+ Yield, LV% 100.0 of the Feed These examples illustrate the ability of both catalysts to upgrade partially reformed naphtha. Incorporation of zinc improves the liquid product selectivity, apparently by reducing dealkylation of existing aromatics. Example 9 Comparison of Unsulfided and Sulfided Platinum Boron Beta The borosilicate version of Beta was impregnated with Pt(NH3)4"2N03 as in Example 4. The catalyst was sulfided at 950°F for 1 hour in the presence of hydrogen. Products 2.9 4.5 0.1 0 13.3 11.6 0.5 0 0 0 22.7 23.8 0 0 26.4 31.4 101.0 101.0 86.0 89.0 -17- / J I 4 4 01 02 Test, conditions were: 03 Temperature = 800°F 04 H2/HC Molar Ratio = 6.4 05 06 WHSV 6 07 Unsulfided Pt/(B)beta Sulfided Pt/(B)beta 08 09 Pressure, psig 200 200 200 200 10 Time, hrs. 3 18 3 18 11 Feed Conversion, % 96.9 95.8 79.1 81.6 12 Cg+ Yield, wt. % 37.6 40.2 59.4 57.0 13 Calculated RON 93.0 92.8 87.5 88.4 14 Aromatization 19.4 21.3 35.2 34.0 15 16 Selectivity, % 17 18 Example 10 19 Comparison of Sulfided Pt/(B)beta and 20 21 Sulfided Pt/(B)beta with 52% Si02 Binder 22 23 800°F, 200 psig, 6 WHSV, 6. 4 H2:HC 24 25 Pt/(B)beta Bound Pt/(B)beta 26 27 Time, hrs. 3 18 3 18 28 Peed Conversion, % 79. 1 81.6 52.7 57.7 29 Cg+ Yield, wt. % 59. 4 57.0 86.5 82.1 30 Calculated RON 87. 5 88.4 79.5 80.2 31 Aromatization 35. 2 34 .0 52.9 47.0 32 Selectivi ty 33 34 -18- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2344 16 800°F, 50 psig, 6 WHSV, 6.4 H2:HC Pt/(B: (beta Bound Pt/(B)beta Time, hrs. 3 18 3 18 Feed Conversion, % 87.9 86.5 62.6 61.5 Cg+ Yield, wt. % 64.3 66.0 84.4 85.0 Calculated RON 97 .8 96.5 84.4 83.7 Aromatization 50.8 51.5 56.3 55.5 Selectivity Example 11 Comparison of Sulfided Pt/(B)beta and Sulfided Pt/Cs-(Al)-(B)beta 8000F, 200 psig, 6 WHSV, 6.4 H2:HC* Pt/(B)beta Pt/Cs-(Al)-(B) beta Feed Conversion, % 79.6 48.0 C5+ Yield, wt. % 59.7 93.7 Calculated RON 87.9 77.0 Propane + Butanes, 18.8 2.3 wt. % Toluene, wt. % 25.6 25.9 Arom. Selectivity 35.7 56.0 *Data averaged for first five hours. -19- n ' N .J i ' 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 28 29 30 31 32 33 34 25 4 4 i § 800 °F, 50 psig, 6 WHSV, 6.4 H2:HC** Pt/(B)Beta Pt/Cs-(Al) -(B )beta Time, hrs. 3 18 3 18 Feed Conversion, % 87.9 86.5 46.0 40.0 C^+ Yield, wt. % 64.3 66.0 95.0 96.0 Calculated RON 97.8 96.5 77.0 74.5 Arom. Selectivity 50.8 51.5 59.5 58.0 Propane + Butanes, 31.4 28.1 3.3 2.5 wt. % Toluene, wt. % 42.0 41.8 26.0 22.0 **Interpolated data. Example 12 Preparation and Testing of Pt- •Boron-SSZ-31 26 , "> mesh ^ 27 The borosilicate version of SSZ-31 was prepared for use as a reforming catalyst. The zeolite powder was impregnated with Pt(NH^)^"2NO^ to give 0.7 wt. % Pt. The material was calcined up to 600°F in air and maintained at this temperature for three hours. The powder was pelletized on a Carver press at 1000 psi, broken, and screened to 24-40 Pt-Boron-SSZ-31 was tested for reforming using an iC^ feed mixture (Philips Petroleum Company) as follows: -20- </div>

Claims

<div id="claims" class="application article clearfix printTableText"> 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 234 4 Reaction Conditions Run 1 Run 2 Temperature, °F 800 800 Total pressure, psig 200 50 l^/Hydrocarbon Mole Ratio 6.4 6.4 Feed rate, WHSV, hr 6 6 Results Feed Run 1 Run 2 Conversion, % 0 68.1 69.7 Aromatization Select. 0 39.4 54.7 Toluene, wt. % 0.7 24.6 36.0 C5-C8 Octane, RON 63.9 82.8 87.6 -21- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 2.3441 6 WHAT IS CLAIMED IS-; WHAT if WE CLAIM IS :

1. A catalytic reforming process which comprises contacting a hydrocarbonaceous feedstream under catalytic reforming conditions with a composition comprising large-pore borosilicate zeolites having a pore size greater than 6 and less than 8 angstroms, with the proviso that the large-pore borosilicate zeolite is not SSZ-33.

2. A process in accordance with Claim 1 wherein said large-pore borosilicate zeolites contain less than 1000 parts per million aluminum.

3. A process in accordance with Claim 2 wherein said large-pore borosilicate zeolites are boron beta zeolite, boron SSZ-24 and boron SSZ-31.

4. A process in accordance with Claims 1, 2 and 3 wherein the boron in the large-pore borosilicate zeolites is partially replaced by a Group IIIA metal, or a first row transition metal.

5. A process in accordance with Claim 4 wherein the replacing metal is cobalt, zinc, aluminum, gallium, iron, nickel, tin and titanium.

6. A process in accordance with Claims 1, 2, 3 and 4 wherein the hydrogenation/dehydrogenation component of said large-pore borosilicate zeolites is a Group VIII metal.

7. A process in accordance with Claim 6 wherein the hydrogenation/dehydrogenation component of said large-pore borosilicate zeolite comprises platinum. -22- j V ' 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 1 6

8. A process in accordance with Claim 6 wherein said large-pore borosilicate zeolite contains an alkali metal component.

9. A process in accordance with Claims 1, 2, 3 and 4 wherein the hydrogenation/dehydrogenation component of said large-pore borosilicate zeolite comprises rhenium and platinum.

10. A process in accordance with Claims 1, 2, 3 and 4 wherein the hydrogenation/dehydrogenation component of said large-pore borosilicate zeolites comprises platinum and tin.

11. A process in accordance with Claims 1, 2 and 3 comprising using a fixed, moving or fluid bed reformer.

12. A process in accordance with Claims 1, 2 and 3 which is a multi-stage catalytic reforming process.

13. A process in accordance with Claim 12 where the large-pore borosilicate zeolite is used in the last reactor to convert the remaining light paraffins not converted by the Pt Re/A^O^ or Pt Sn/A^O^ catalysts used in the upstream reactors.

14. A process in accordance with Claim 12 where the large-pore borosilicate zeolite is used in the last stage of a multi-stage catalytic reforming process where the operating pressure of the last stage is much -lower than the upstream stage. -23- 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 23 4 4 1 A process in accordance with Claim 1 wherein the feedstream contains less than 1 part per million' sulfur. A process as claimed in any one of the preceding claims when performed substantially as hereinbefore described with reference to any example thereof. A reform product produced by a process as claimed in any one of the preceding claims. ^— DATED THIS C^ri DAY OF 19 90 ■' A-J- a PER AGENTS FOR THE APPLICANTS -24- </div>