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