PROCESS FOR PRODUCING LOW AROMATIC DIESEL FUEL WITH HIGH CETANE INDEX

Abstract: A process for converting at least one olefin and at least one paraffin to a diesel fuel blending component comprises the steps of contacting said olefin and said isoparaffin with a catalyst selected from the group consisting of MCM-22, MCM-36, MCM-49, MCM-56 and MCM-58 to provide a product containing a diesel fuel.

Description: PROCESS FOR PRODUCING LOW AROMATIC DIESEL FUEL WITH HIGH CETANE INDEX The present invention relates to a process for producing low aromatic diesel fuel with a high cetane index. Recent regulatory developments have led refiners to seek methods for reformulating motor fuels, including gasoline and diesel fuel, to meet increasingly stringent air quality requirements. These techniques include reducing the olefin and aromatic content of the motor fuels while maintaining the desired operational characteristics as predicted by the octane or cetane rating of the fuel. Alkylation is a reaction in which an alkyl group is added to an organic molecule. Thus an isoparaffin can be reacted with an olefin to provide an isoparaffin of higher molecular weight. Industrially, the concept depends on the reaction of a C_ to C_ olefin with isobutane in the presence of an acidic catalyst producing a so-called alkylate. Industrial alkylation processes have historically used large volumes of liquid Bronsted acid catalysts such as hydrofluoric or sulfuric acid under relatively low temperature conditions. Acid strength is preferably maintained at 88 to 94 weight percent by the continuous addition of fresh acid and the continuous withdrawal of spent acid. Liquid acid catalyzed isoparaffin:olefin alkylation processes share inherent drawbacks including environmental and safety concerns, acid consumption, and sludge disposal. For a general discussion of sulfuric acid alkylation, see the articles by L.F. Albright et al., "Alkylation of Isobutane with C Olefins", 27 Ind. Eng. Che . Res. , 381-397, (1988). For a survey of hydrofluoric acid catalyzed alkylation, see Handbook of Petroleum Refining Processes 23-28 (R.A. Meyers, ed. , 1986). According to the inventon, there is provided a process for converting at least one olefin and at least one paraffin to a diesel fuel blending component comprising the steps of contacting said olefin and said isoparaffin with a catalyst containing at least one material selected from the group consisting of MCM-22, MCM-36, MCM-49, MCM-56 and MCM- 58 to provide a product comprising diesel fuel. Feedstocks The feed olefins can come from among many sources including FCC olefins, the by-products of catalytic dewaxing operations and the olefinic gasoline boiling range fraction from a delayed coker unit. A detailed description of possible olefins sources is outlined in U.S. Patent 5,227,552. Preferably the olefinic feedstock comprises C 2 - C 10 olefins and most preferably C 3 -C 8 olefins. The isoparaffin can come from FCC, hydrocracking, etc. process or by isolation of field production off-gases. Generally, C 4 -C 8 isoparaffins and preferably C 4 -C 5 isoparaffins are used in the process of the invention. Process Conditions The conditions which can be used in the process of the invention are generally as follows: Broad Range Preferred Range Temperature 100-500°F 200-400°F Pressure 0-1500 psig 50-1000 psig LHSV 0.01-10 0.1-5.0 Olefin:Paraffin 0.1-100 0.25-50 Molar Ratio in Feedstock The reaction temperature can be varied to obtain a range of aromatics content in the diesel fuel. To produce a diesel range blending stock containing less than about 10 wt% aromatics, the reactor temperature is preferably kept below about 375 °F. To meet the 35 wt% aromatics limit set by the US Environmental Protection Agency (EPA) , reactor temperature is preferably controlled below about 440 °F. In a preferred embodiment, the process conditions are controlled to produce a distillate product containing less than about 35 weight percent aromatics, and more preferably less than about 10 weight percent aromatics. In general, higher cetane index of the diesel range product is favored by higher olefin WHSV and lower temperatures. However, products produced over a broad range of conversion conditions useful in the present process exceeded a cetane index of 35, and typically met the US EPA minimum of 40 cetane index. Under preferred conversion conditions, the distillate product cetane index was 45 or higher. Conversion is inversely proportional with WHSV olefln on zeol i te for a given temperature. Between 0.1 and 1.0 WHSV, reactor temperature must be above about 350 °F in order to achieve C 5 -olefin conversions above 90%. If temperature is restricted to 375 °F to limit aromatics to 10 wt%, WHSV olefin on zeol i te must be held below about 0.3 to maintain 90% or greater pentenes conversion. The term "yield" as used herein is defined as the weight of product per weight of converted olefin. Total product yields above unity indicate that isoparaffin has been incorporated into the products. Maximum gasoline yield in isobutane/butene alkylation results from combination of one mole of each reactant to provide a yield slightly above 2.0. Ideally, a diesel range fuel is produced by reacting more than one mole of olefin per isoparaffin. For instance, a mole of isobutane must combine with two or three moles of butene to reach sufficient molecular weight to enter the boiling range of diesel fuel. Likewise, a mole of isopentane would require two moles of pentene to reach diesel range and would give a yield of about 1.5. Therefore, diesel production in the present invention a lower isoparaffin/olefin molar ratio than typically is used for producing gasoline from a similar reactor feed stream. Reaction products boiling at a cut point up to about 450°F may be recycled to the contacting step. Preferably, reaction products boiling at a cut point up to about 390°F may be recycled to the contacting step. Catalysts The catalysts useful in the present invention comprise one or more members of the group consisting of MCM-22, MCM- 36, MCM-49, MCM-56 and MCM-58. Preferably, the catalyst is MCM-56. MCM-22 is taught in U.S. Patents 4,992,615; 5,012,033; 5,073,665 and 5,107,047. MCM-36 is taught in U.S. Patents 4,250,277; 5,258,569 and 5,292,698. MCM-49 is taught in U.S. Patents 5,236,575; 5,254,792 and 5,354,718. MCM-56 is taught in U.S. Patent 5,362,697. MCM-58 is taught in International Publication No. W095/11196. The invention will now be more particularly described with reference to the accompanying examples. Example 1 The catalyst used in this example was an extrudate of the hydrogen-form of MCM-56 (65%) in an alumina binder (35%) . The catalyst was loaded into a stainless steel tubular reactor and bracketed by vycor chips which served as heat exchangers. After placing the reactor in a tube furnace, the catalyst was dried by heating for at least two hours to at least 300 °F in a stream of flowing nitrogen. The reactor temperature was adjusted to 370 °F at 600 psig, and filled with isobutane. A pre-mixed isobutane/butene-2 feed stream (molar ratio = 1) then was introduced at a flow rate of 0.57 gm butene/g MCM-56/hr. After passing pre- mixed feed through the reactor zone for 49 hrs, product was collected over the following 28 hrs. Product distributions were calculated from gas chromatographic (gc) analyses of the gaseous and liquid products, and an additional simulated distillation ASTM 2887 of the liquid products. The total reactor effluent weight was 58.7 g (97.7% mass balance) and showed the following distribution: Conversion of total butenes was 97.1%. Calculated yields of C5-plus components per butenes converted (wt/wt) were: Fraction Yields C 5 0.08 C 6 -300 °F 0.51 300 - 400 °F 0.21 400 - 650 °F 0.30 above 650 °F 0.04 Total 1. 14 About 25 g of squalane was added to a portion of the liquid product (34.6 g) to serve as a high boiling "chaser" during fractional microdistillation. After distilling the sample to a 300 °F endpoint at ambient atmospheric pressure, the residua were fractionated under vacuum (about 55 torr) to obtain a cut (4.3 g) with the intended kerojet boiling range from 300 °F to 400 °F. The actual boiling range for this cut was estimated by simulated distillation analysis ASTM 2887. The boiling range and product properties for this sample were: Intended cut 300-400 °F Boiling Range (°F) BP 218 T10 237 T50 353 T90 403 End Point 459 API gravity 54.3 Cetane Index 53 Cetane Number ( X H nmr) 19 After cooling, the residua were again distilled under vacuum (about 1 -2 torr) to obtain a cut (9.4 g) with the intended diesel fuel boiling range from 400 °F to 650°F. The actual boiling range for this cut was estimated by simulated distillation analysis ASTM 2887. The boiling range and product properties for this sample were: Intended cut 400- ■ 650°F Boiling Range ( 6 F) IBP 330 T10 386 T50 473 T90 581 EP 655 API gravity 42.6 Cetane Index 55 Cetane Number ( X H nmr) 19 wt% Aromatics 8.4 Example 2 The process of Example 1 was repeated with the reactor temperature being adjusted to 302 °F at 60Q psig and the pre-mixed isobutane/butene-2 feed stream (molar ratio = 1) being introduced at a flow rate of 1.02 girt butene/gm MCM- 56/hr. After passing pre-mixed feed through the reactor zone for 44.5 hrs, product was collected over the following 24 hrs. Product distributions were determined as in Example 1, with the total reactor effluent weighing 92.4 g (99.3% mass balance) and having the following distribution: Conversion of total butenes was 66.7%. Calculated yields of C5-plus components per butenes converted (wt/wt) were: Fraction Yields c 5 0.01 C 6 -300 °F 0.74 300 - 400 °F 0.22 400 - 650 °F 0.09 above 650 °F 0.00 Total 1.06 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300- ■ 400°F Boiling Range (°F) BP 219 T10 243 T50 320 T90 391 EP 433 API gravity 54.2 Cetane Index 42 Cetane Number (H 1 nmr) 11 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boiling Range <"F) IBP 344 T10 381 T50 456 T90 507 EP 575 API gravity 44.9 Cetane Index 57 Cetane Number ( X H nmr) 15 wt% Aromatics 1.5 Example 3 The process of Example 1 was repeated with the reactor temperature being adjusted to 450 °F at 600 psig and the pre-mixed isobutane/butene-2 feed stream (molar ratio = 1) being introduced at a flow rate of 1 gm butene/gm MCM- 56/hr. After passing pre-mixed feed through the reactor zone for 41.5 hrs, product was collected over the following 23.3 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and an additional simulated distillation ASTM 2887 of the liquid products. The total reactor effluent weight was 88.1 g (99.4% mass balance) and showed the following distribution: Conversion of total butenes was 98.2%. Calculated yields of C 5 -plus components per butenes converted (wt/wt) were: Fraction Yields c 5 0.16 C 6 -300 °F 0.58 300 - 400 °F 0.15 400 - 650 °F 0.24 above 650 °F 0.01 Total 1.13 Following the distillation procedures of Example l, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Roiϋinα Ranσe (°F) BP 194 T10 242 T50 343 T90 406 EP 451 API gravity 55.8 Cetane Index 53 Cetane Number ( X H nmr) 19 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boiling Range (°F ) IBP 334 T10 398 T50 493 T90 610 EP 684 API gravity 39.5 Cetane Index 52 Cetane Number ( 2 H nmr) 25 wt% Aromatics 26.6 Example 4 The procedure of Example 1 was repeated with the reactor temperature being adjusted to 300 °F at 600 psig and the pre-mixed isobutane/butene-2 feed stream (molar ratio = 1) being introduced at a flow rate of 0.11 gm butene/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 313.3 hrs, product was collected over the following 191.5 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and an additional simulated distillation ASTM 2887 of the liquid products. The total reactor effluent weight was 75.6 g (96.2% mass balance) and showed the following distribution: Conversion of total butenes was 98.2%. Calculated yields of C 5 -plus components per butenes converted (wt/wt) were: -12- Fraction Yields c 5 0.02 C 6 -300 °F 0.58 300 - 400 °F 0.30 400 - 650 °F 0.22 above 650 °F 0.00 Total 1.12 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300- ■ 400°F Boiling Ranqe ( F) BP 228 T10 263 T50 380 T90 414 EP 491 API gravity 52.3 Cetane Index 56 Cetane Number e* nmr) 13 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400- 650°F Boiling Range ( 6 F) IBP 356 T10 398 T50 475 T90 550 EP 628 API gravity 44.2 Cetane Index 58 Cetane Number ( α H nmr) 18 wt% Aromatics 2.1 Example 5 The procedure of Example 1 was repeated with the reactor temperature being adjusted to 450 °F at 600 psig and the pre-mixed isobutane/butene-2 feed stream (molar ratio = 1) being introduced at a flow rate of 1 gm butene/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 319.5 hrs, product was collected over the following 159 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and an additional simulated distillation ASTM 2887 of the liquid products. The total reactor effluent weight was 62.8 g (96.2% mass balance) and showed the following distribution: Conversion of total butenes was 99.6%. Calculated yields of C 5 -plus components per butenes converted (wt/wt) were: Fraction Yields c 5 0.21 C 6 -300 °F 0.68 300 - 400 °F 0.19 above 650 °F 0.08 Total 1.43 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boiling Range (°F) BP 137 T10 228 T50 282 T90 385 EP 436 API gravity 60.6 Cetane Index 43 Cetane Number ( H nmr) 28 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boiling Range (°F) IBP 310 T10 386 T50 479 T90 591 EP 655 API gravity 35.8 Cetane Index 44 Cetane Number ( : H nmr) 27 wt% Aromatics 44.3 Example 6 Example was repeated with the reactor temperature being adjusted to 369 °F at 600 psig and the pre-mixed isobutane/butene-2 feed stream (molar ratio = 1) being introduced at a flow rate of 0.5 gm butene/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 74 hrs, product was collected over the following 28.5 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and an additional simulated distillation ASTM 2887 of the liquid products. The total reactor effluent weight was 61.0 g (101.4% mass balance) and showed the following distribution: Conversion of total butenes was 99.6%. Calculated yields of C 5 -plus components per butenes converted (wt/wt) were: Fraction Yields C5 0. 16 C 6 -300 °F 0.66 300 - 400 °F 0.28 400 - 650 °F 0.27 above 650 °F 0.01 Total 1.39 Following the distillation procedures of Example l, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300--400°F Boilinσ Ranσe (°F) BP 219 T10 271 T50 372 T90 407 EP 441 API gravity 52.9 Cetane Index 55 Cetane Number d nmr) 14 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400- -650°F Boiling Range ( 3 F) IBP 344 T10 394 T50 468 T90 555 EP 634 API gravity 43.8 Cetane Index 57 Cetane Number ( : H nmr) 13 wt% Aromatics 4.2 Example 7 Example 1 was repeated but with the reactor being adjusted to a temperature of 377 °F at 600 psig, and filled with isopentane. A pre-mixed isopentane/pentene-1 feed stream (molar ratio = 4.9) was then introduced into the reactor at a flow rate of 0.56 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 5.8 hrs, product was collected over the following 14.0 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 343.5 g (99.5% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 96.4% . Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were: Fraction Yields iC4 0. 19 C . -300 °F 0.42 300 - 400 °F 0. 45 400 - 650 °F 0. 37 . above 650 °F 0. 08 Total 1.51 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boilinσ Ranqe ( » F) BP 222 T10 286 T50 325 T90 363 EP 427 API gravity 57.7 Cetane Index 52 Cetane Number ( X H nmr) 25 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boilinσ Ranσe (°F) IBP 340 T10 410 T50 482 T90 571 EP 625 API gravity 42. Cetane Index 8 Cetane Number ( X H nmr) 57 wt% Aromatics 29 7.1 Example 8 Example 7 was repeated with the reactor temperature being adjusted to 304 °F at 600 psig and a pre-mixed isopentane/pentene-1 feed stream (molar ratio = 9.8) being introduced at a flow rate of 1.01 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 6.2 hrs, product was collected over the following 4.0 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 330.7 g (100.6% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 21.5%. Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were: Fraction Yields iC4 0. 09 C 6 -300 °F 0. 18 300 - 400 °F 1. 09 400 - 650 °F 0.47 above 650 °F 0. 00 Total 1. 83 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boiling Range (°F) BP 193 T10 306 T50 328 T90 341 EP 446 API gravity 55. Cetane Index 0 Cetane Number ( α H nmr) 46 14 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boiling Range (°F) IBP 302 T10 326 T50 467 T90 519 EP 785 API gravity 44.6 Cetane Index 58 Cetane Number ( X H nmr) 23 wt% Aromatics <5 Example 9 Example 7 was repeated with the reactor temperature being adjusted to 449 °F at 600 psig and a pre-mixed isopentane/pentene-1 feed stream (molar ratio = 9.9) being introduced at a flow rate of 0.99 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 19.8 hrs, product was collected over the following 3.5 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 282.7 g (99.0% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 86.9%. Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were: Fraction Yields iC4 0.26 C . -300 °F 0.57 300 - 400 °F 0.29 400 - 650 °F 0.25 above 650 °F 0. 03 Total 1.40 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300--400°F Boilinσ Ranσe (' J F) BP 173 T10 267 T50 324 T90 375 EP 444 API gravity 55.0 Cetane Index 45 Cetane Number (' H nmr) 17 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400- -650°F Boilinα Ranσe ( J F) IBP 315 T10 371 T50 471 T90 564 EP 634 API gravity 38.2 Cetane Index 47 Cetane Number ( ] H nmr) 25 wt% Aromatics 46.7 Example 10 Example 7 was repeated with the reactor temperature being adjusted to 444 °F at 600 psig and a pre-mixed isopentane/pentene-1 feed stream (molar ratio = 1.0) being introduced at a flow rate of 0.10 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 87.3 hrs, product was collected over the following 48.2 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent -24- weight was 72.1 g (100.1% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 99.2%. Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were: Fraction Yields iC4 0.21 C . -300 °F 0.42 300 - 400 °F 0.46 400 - 650 °F 0. 09 above 650 °F 0. 01 Total 1. 19 Following the distillation procedures of Example 1, the boiling range and product properties of the intended keroj t boiling range cut were: Intended cut 300-400°F Boilinσ Ranαe (°F) BP 133 T10 235 T50 322 T90 381 EP 439 API gravity 56.9 Cetane Index 49 Cetane Number ϋ nmr) 31 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boilinσ Ranσe (°F ) IBP 311 T10 385 T50 488 T90 592 EP 659 API gravity 33.3 Cetane Index 41 Cetane Number CH nmr) 28 wt% Aromatics 45.9 Example 11 Example 7 was repeated with the reactor temperature being adjusted to 374 °F at 600 psig and a pre-mixed isopentane/pentene-1 feed stream (molar ratio = 4.9) being introduced at a flow rate of 0.56 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 8.0 hrs, product was collected over the following 14.5 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 358.7 g (100.4% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 65.6%. Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were: Fraction Yields iC4 0. 06 C 6 -300 °F 0. 53 300 - 400 °F 0. 16 400 - 650 °F 0.21 above 650 °F 0. 11 Total 1. 07 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 400-650°F Boilinσ Ranσe (°F) IBP 311 T10 385 T50 488 T90 592 EP 659 API gravity 33.3 Cetane Index 41 Cetane Number ( X H nmr) 28 wt% Aromatics 45.9 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boiling Range ('F ) IBP 314 T10 367 T50 466 T90 539 EP 633 API gravity 39.2 Cetane Index 48 Cetane Number ( α H nmr) 18 wt% Aromatics 9.1 Example Example 7 was repeated with the reactor temperature being adjusted to 297 °F at 600 psig and a pre-mixed isopentane/pentene-1 feed stream (molar ratio = 1.0) being introduced at a flow rate of 0.10 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 77.5 hrs, product was collected over the following 49.0 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 80.5 g (98.7% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 98.7%. Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were: Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boilinσ Ranσe ( ϋ F) BP T10 132 T50 246 T90 326 EP 378 453 API gravity 55.7 Cetane Index 48 Cetane Number ( X H nmr) 17 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boiling Range (°F) IBP 308 T10 370 T50 487 T90 589 EP 656 API gravity 41.0 Cetane Index 54 Cetane Number H nmr) 21 wt% Aromatics 7.8 Example 13 Example 7 was repeated with the reactor temperature being adjusted to 296 °F at 600 psig and a pre-mixed isopentane/pentene-1 feed stream (molar ratio = 9.8) bein introduced at a flow rate of 0.10 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 43.0 hrs, product was collected over the following 55.0 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 503.7 g (100.3% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 33.2% . Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were: Fraction | Yields iC4 0. 06 C . -300 °F 0.24 300 - 400 °F 1. 06 400 - 650 °F 0. 30 above 650 °F 0. 00 Total 1. 66 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boilinσ Ranσe (°F) BP 208 T10 302 T50 327 T90 343 EP 454 API gravity 55.8 Cetane Index 48 Cetane Number R nmr) 16 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boiling Range ( U F) IBP 300 T10 324 T50 461 T90 507 EP 597 API gravity 46.3 Cetane Index 60 Cetane Number ( X H nmr) 20 wt% Aromatics <5 Example 14 Example 7 was repeated with the reactor temperature being adjusted to 377 °F at 600 psig and a pre-mixed isopentane/pentene-1 feed stream (molar ratio = 5.0) being introduced at a flow rate of 0.54 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 18.0 hrs, product was collected over the following 6.0 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 165.4 g (101.0% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 94 .5% . Calculated yields of isobutane and C 6 -plus components per C 6 -olefins converted (wt/wt) were: Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boilinq Range ( ϋ F) BP 164 T10 269 T50 316 T90 351 EP 428 API gravity 57.7 Cetane Index 49 Cetane Number n nmr) 26 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boilinσ Ranσe ( ϋ F) IBP 302 T10 372 T50 471 T90 575 EP 636 API gravity 43.3 Cetane Index 56 Cetane Number ( H nmr) 27 wt% Aromatics 7.1 Example 15 Example 7 was repeated with the reactor temperature being adjusted to 302 °F at 600 psig and a pre-mixed isopentane/pentene-1 feed stream (molar ratio = 1.0) being introduced at a flow rate of 1.00 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 18.0 hrs, product was collected over the following 6.0 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 102.2 g (103.1% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 23.9%. Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were: Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boilinσ Ranσe (°F) BP 213 T10 318 T50 332 T90 346 EP 418 API gravity 54.6 Cetane Index 47 Cetane Number ( X H nmr) 16 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boilinα Ranσe (*F ) IBP 309 T10 325 T50 474 T90 498 EP 589 API gravity 45.3 Cetane Index 61 Cetane Number e * nmr) 22 wt% Aromatics 5.1 Example 1$ Example 7 was repeated with the reactor temperature being adjusted to 458 °F at 600 psig and a pre-mixed isopentane/pentene-1 feed stream (molar ratio = 1.0) being introduced at a flow rate of 1.01 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 17.5 hrs, product was collected over the following 7.0 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 115.7 g (99.9% mass balance) and showed the following distrib tion: Conversion of total C 5 -olefins was 98.6% . Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were: Fraction Yields iC4 0.13 C6-300 °F 0.36 300 - 400 °F 0.27 400 - 650 °F 0.30 above 650 °F 0. 12 Total 1. 17 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boilinσ Ranσe ( ϋ F) BP 185 T10 276 T50 330 T90 382 EP 445 API gravity 56.7 Cetane Index 51 Cetane Number ( X H nmr) 32 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400- 650°F Boiling Range ( ώ F) IBP 315 T10 395 T50 495 T90 596 EP 652 API gravity 38.3 Cetane Index 51 Cetane Number ( X H nmr) 31 wt% Aromatics 28.8 Example 17 Example 7 was repeated with reactor temperature being adjusted to 450 °F at 600 psig and a pre-mixed isopentane/pentene-1 feed stream (molar ratio = 9.8) being introduced at a flow rate of 0.10 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 21.0 hrs, product was collected over the following 41.5 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 384.0 g (99.3% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 97.0% . Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were : Fraction Yields iC4 0.56 C 6 -300 °F 0.70 300 - 400 °F 0.36 400 - 650 °F 0.28 above 650 °F 0. 05 Total 1.96 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boiling Range (°F) BP 166 T10 269 T50 327 T90 379 EP 454 API gravity 57.2 Cetane Index 51 Cetane Number ( α H nmr) 33 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boiling Range ("F " ) IBP 302 T10 360 T50 472 T90 577 EP 646 API gravity 38.0 Cetane Index 47 Cetane Number ( α H nmr) 32 wt% Aromatics 37.5 Example 18 Example 7 was repeated with the reactor temperature being adjusted to 374 °F at 600 psig and pre-mixed isopentane/pentene-1 feed stream (molar ratio = 4.8) being introduced at a flow rate of 0.56 gm pentenes/gm MCM-56/hr. After passing pre-mixed feed through the reactor zone for 50.5 hrs, product was collected over the following 6.5 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and a simulated distillation ASTM 2887 of the residua after rotory evaporation (85 °C, ambient atmospheric pressure) of the total liquid products. The total reactor effluent weight was 181.3 g (101.0% mass balance) and showed the following distribution: Conversion of total C 5 -olefins was 42.6% . Calculated yields of isobutane and C 6 -plus components per C 5 -olefins converted (wt/wt) were: Fraction Yields iC4 0.12 C 6 -300 °F 0.19 300 - 400 °F 0.83 400 - 650 °F 0.12 above 650 °F 0.00 Total 1.26 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boilinσ Ranαe (°F) BP 158 T10 298 T50 330 T90 351 EP 468 API gravity 54.9 Cetane Index 47 Cetane Number On nmr) 13 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boilinσ Ranσe (°F) IBP 293 T10 323 T50 455 T90 496 EP 587 API gravity 46.2 Cetane Index 59 Cetane Number u nmr) 21 wt% Aromatics 16.1 Example 19 The catalyst used in this example was an extrudate of the proton-form of MCM-58 (65%) in an alumina binder (35%) . The catalyst (15.65 g) was loaded into a stainless steel tubular reactor and bracketed by vycor chips which served as heat exchangers. After placing the reactor in a tube furnace, the catalyst was dried by heating for at least two hours to at least 300 °F in a stream of flowing nitrogen. The reactor temperature was adjusted to 297 °F at 600 psig, and filled with isopentane. A pre-mixed isopentane/pentene-1 feed stream (molar ratio = 9.7) then was introduced at a flow rate of 0.1 gm pentenes/gm MCM- 58/hr. After passing pre-mixed feed through the reactor zone for 22.5 hrs, product was collected over the following 28 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and an additional simulated distillation ASTM 2887 of the liquid products. The total reactor effluent weight was 307.2 g (99.6% mass balance) and showed the following distribution: Conversion of total pentenes was 55.7%. Calculated yields of isobutane and C 6 -plus components per pentenes converted (wt/wt) were: About 25 g of squalane was added to a portion of the liquid product (39 g) to serve as a high boiling "chaser" during fractional microdistillation. After distilling the sample to a 300 °F endpoint at ambient atmospheric pressure, the residua were fractionated under vacuum (about 55 torr) to obtain a cut (12.3 g) with the intended kerojet boiling range from 300 °F to 400 °F. The actual boiling range for this cut was estimated by simulated distillation analysis ASTM 2887. The boiling range and product properties for this sample were: Intended cut 300- -400 °F Boilinσ Ranσe T F) IBP 202 T10 299 T50 328 T90 358 EP 460 API gravity 55.6 Cetane Index 48 Cetane Number (H 1 nmr) 20 After cooling, the residua were again distilled under vacuum (about 1 -2 torr) to obtain a cut (13.9 g) with the intended diesel fuel boiling range from 400 °F to 650°F. The actual boiling range for this cut was estimated by simulated distillation analysis ASTM 2887. The boiling range and product properties for this sample were: Intended cut 400-650°F Boiling Range TF) IBP 308 T10 375 T50 475 T90 578 EP 630 API gravity 45.7 Cetane Index 62 Cetane Number (H 1 nmr) 29 wt.% Aromatics 1.7 Example 20 Example 19 was repeated with the reactor temperature being adjusted to 350 °F at 600 psig. After passing the isopentane/pentene-1 pre-mixed feed through the reactor zone for 48.3 hrs, product was collected over the following 25.8 hrs. Product distributions were calculated from gc analyses of the gaseous and liquid products, and an additional simulated distillation ASTM 2887 of the liquid products. The total reactor effluent weight was 288.1 g (99.7% mass balance) and showed the following distribution: Conversion of total pentenes was 94.7%. Calculated yields isobutane and C 6 -plus components per pentenes converted (wt/wt) were: Fraction Yields c 5 0.04 C . -300 °F 0.28 300 - 400 °F 0.38 400 - 650 °F 0.54 above 650 °F 0.04 Total 1.28 Following the distillation procedures of Example 1, the boiling range and product properties of the intended kerojet boiling range cut were: Intended cut 300-400°F Boilinσ Range (°F) BP 143 T10 270 T50 320 T90 348 EP 440 API gravity 59.5 Cetane Index 55 Cetane Number (H 1 nmr) 31 and the boiling range and product properties for the intended diesel fuel boiling range cut were: Intended cut 400-650°F Boilinσ Ranσe (°F) IBP 309 T10 380 T50 490 T90 600 EP 672 API gravity 46.5 Cetane Index 65 Cetane Number (H_ nmr) 33 wt% Aromatics 0.8

Claims: What is claimed is: 1. A process for converting at least one olefin and at least one paraffin to a diesel fuel blending component comprising the steps of contacting said olefin and said isoparaffin with a catalyst containing at least one material selected from MCM-22, MCM-36, MCM-49 MCM-56 and MCM-58 to provide a product comprising diesel fuel. 2. The process of claim 1, wherein said catalyst comprises MCM-56. 3. The process of claim 1, wherein said catalyst comprises MCM-58. 4. The process of claim 1, wherein said conversion conditions include a temperature in the range of from about 100-500°F; a pressure in the range of from about 0 to about 1500 psig; an olefin WHSV (on zeolite basis) in the range of from about 0.01 to 10; and an isoparaffin:olefin molar ratio in the feedstock in the range of from about 0.1-100. 5. The process of claim 1, wherein said conversion conditions include a temperature in the range of from about 200-400°F; a pressure in the range of from about 50 to about 100 psig; an olefin WHSV (on zeolite basis) in the range of from about 0.1 to 5; and an isoparaffin:olefin molar ratio in the feedstock in the range of from about 0.25 to about 50. 6. The process of claim 1, wherein said at least one olefin is selected from C 3 -C 10 olefins. 7. The process of claim 6, wherein said at least one olefin is selected from C 4 -C 8 olefins. 8. The process of claim 1, wherein said at least one isoparaffin is selected from C 4 -C 8 isoparaffins. 9. The process of claim 8 wherein said at least one isoparaffin is selected from C 4 -C 5 isoparaffins.

Inventors: HELLRING STUART DAMON, HUSS ALBIN JR, KRESGE CHARLES THEODORE, LANDIS MICHAEL EUGENE, MARLER DAVID OWEN, TEITMAN GERALD JOSEPH, TIMKEN HYE KYUNG CHO, TREWELLA JEFFREY CHARLES, VALYOCSIK ERNEST W, HELLRING, STUART, DAMON, HUSS, ALBIN, JR., KRESGE, CHARLES, THEODORE, LANDIS, MICHAEL, EUGENE, MARLER, DAVID, OWEN, TEITMAN, GERALD, JOSEPH, TIMKEN, HYE, KYUNG, CHO, TREWELLA, JEFFREY, CHARLES, VALYOCSIK, ERNEST, W.
Applicants: MOBIL OIL CORP, MOBIL OIL CORPORATION
Application year: 1996
Main classification: C07C2
IPC codes: B01J29, C07B61, C07C2, C07C5, C07C9, C10G11