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Computation of Petroleum Fractionation

Estimation of A. S. T. M. Distillation Curves from True-BoilingPoipt Distillation Analvses

J

R. L. GEDDES

Stone & Webster Engineering Corporation, Boston, Mass.

OR the cases of fractiona- tion of relatively simple Fmixtures of the lower boil-

ing hydrocarbons into specified products, the methods of compu- tation of the number of bubble trays and the reflux ratios re- quired have been developed until they constitute a practical tool for engineering design. The use of similar methods in fractiona- tion problems involving the higher boiling, exceedingly com- plex petroleum mixtureshas been hampered by the lack of a precise method of interpreting the calcu- lated true-boiling-point analyses

of productsin terms of theempiri- cal A. S. T. M. distillation analy- sis (1). The latter convenient-inspection assay, by long usage in the art of commercial fractionation, forms the practical criterion for definition of quality of naphthas, gasolines, and kerosenes, and of degree of separation between fractions. Rigorous means are available for computation of the frac- tionation requirements for complex petroleum mixtures (5, 9),the calculated product fractions being defined by true- boiling-point curves. The present paper offers an improved method of estimating the corresponding A. S. T. M. distillation curves. Nelson and Hamburg (6)published a method of correlation of A. S. T. M. and true-boiling-point distillation curves, but their correlation does not appear to give suf- ficiently precise results (see also Lewis and Robinson, 4). During the course of many laboratory research projects and commercial plant performance tests over a period of several years, there became available a large number of true- boiling-point analyses of petroleum fractions for which the corresponding A. S. T. M. distillation data (1) had been ob- tained. The true-boiling-point distillations were made with a Podbielniak standard high-temperature fractionation column (7). The present correlation work is based upon a survey of the data from approximately two hundred samples; Table I summarizes part of the basic data used. Both the true-boiling-point and A. S. T. M. distillation curves are the results of plotting as the abscissa the volume percentage of the sample distilled against the still-head tem- perature as the ordinate. The A. S. T. M. procedure involves simple batch distillation with no added fractionation except that due to a slight amount of partial condensation in the upper parts of the distillation flask. The true-boiling-point (T. B. P.) distillation, on the other hand, involves a fairly

The estimation of A. S. T. M. distillation curves from true-boiling-point distillation curves is a practical problem in the inter- pretation of theoretical computations of petroleum fractionation. The present paper offers an improved method of esti- mation of the A. S. T. M. curve from the true-boiling-point curve, based on a survey of data from a large number of distillation analyses. It is indicated that the same correlation may be used conversely for approximate estimation of the true- boiling-point curve corresponding to a given A. S. T. M. distillation curve.

efficient column fractionation of a sample. A few general characteristics of the A. S. T. M. distillation procedure and curve may be noted. This batch distillation test is empirical, and the exact nature of the curve obtained depends upon the experimental technique followed. A stand- ardized procedure is specified (I), but within the range of permissible operation several slightly different but acceptable distillation curves may be ob- tained for a given sample of oil. Under certain conditions super-

heating leads to incorrect vmor temperature readings. The dis- tillation curve approaches but is not the same as that obtained in true differential vaporization, largely because of partial con- densation in the neck of the distillation flask, lack of true equi- librium between vapor and liquid, and the liquid holding ca- pacity of the condensing system. The degree of fractionation is intermediate between that of an equilibrium flash distillation and a T. B. P. distillation, and the slope of a given portion of the A. S. T. M. curve depends not only upon the slope of the corre- sponding portion of the T. B. P. curve, but also on the slope and character of the other parts of the latter. These considera- tions lead to the expectation that any statistical correlation of A. S. T. M. and T. B. P. distillation curves will involve con- siderable scattering of the experimental points. However, it also follows that a rational correlation, once effected, might permit a more reliable estimation of the “best” A. S. T. M. curve than would be obtained experimentally from a single actual distillation test. For a given sample of oil the exact character of the T. B. P. curve depends upon the effectivenessof the column fractiona- tion used. Just what minimum degree of fractionation con- stitutes a T. B. P. fractionation is not precisely dehed in the literature, but this is usually determined by the use to be made of such an analysis. By way of illustration, if we carry out a series of successive batch column fractionations on a given sample, starting with a degree of fractionation less than T. B. P. requirements and increasing the power of the frac- tionation, the first distillation curves of the series will be smooth and will be characterized by increasing slope until a limiting value of the latter is attained. With subsequent in- creased fractionation, stairsteps in the curve will develop, but even with the highest attainable fractionation the position

795

796

Sample

NO.

1

2

3

4

5

6

7

8

9

Name

Rubber solvent

Na htha

V. 8.& P. naphtha

Stoddard solvent

Naphtha

Naphtha

Kerosene

Gas oil

Naphtha

Blend

10

11 Blend

12

13

14

15

16

17

18

19

20

21

22

23

24

Gas oil

Blend

Naphtha

Gasoline

Naphtha

Xaphtha

Unstripped naphtha

Unstripped kerosene

Unstripped gas oil

Gas oil

Unstripped naphtha

Unstripped kerosene

Unstripped gas oil

Gas oil

26

26

27

28 Gas oil

29 Blend

30 Cracked yaso:ir.e

31 Crackcd gasoline

32 Crscked nnp!itha
33

Cracked

nnplithn

34 Cr.ickc-d nnpLrha

35 Polymer gasoline
36

Polymer gasoline

37 Polymer gasoline

38 Polymer gasoline

39 Polymer gasoline

40 Light naphtha

41 Light naphtha

42 Light naphtha

43 Light naphtha

44 Light naphtha

45 Heavy naphtha

46 Heavy naphtha
47

48 Gasbil

49 Aromatic extract

50 Gas oil

51 Gasoline

52 Naphtha

53 Naphtha
54

55 Naphtha

56 Kerosene

57 Kerosene

58 Gas oil

Kaphtha

Unstri

NaphtRa

ped kerosene

Kerosene

Volume per cent

INDUSTRIAL

A. P.

I.

Gravity

77.2

66.6

61.2

54.1

61.6

47.4

41.0

34.7

57.6

50.6

46.3

37.6

38.9

42.6

62.1

67.7

56.3

47.9

41.5

35.5

30.0

48.4

41.4

35.5

31.0

43.6

51.4

28.5

52.6

39.1

34.5

34.8

34.4

31.5

58.7

57.5

61.7

59.4

61.4

74:5

74.2

77.8

80.8

52.1

48.6

39.7

34.5

14.8

32.9

63.5

55.1

51.9

50.8

48.8

47.0

44.9

42.8

1.B.P:

117

158

220

324

100

318

381

456

113

126

139

387

340

332

128

117

238

287

339

349

465

296

345

352

469

331

231

405

102

100

124

183

181

184

98

98

96

96

94

82

94

95

87

73

266

265

347

483

431

555

97

199

178

308

324

344

366

382

AND

TABLEI.

ENGINEERING

CHEMISTRY

DISTILLATIONDATA

A. 9. T. M. Distillation (Corrected for Loss),

10%.

143

181

240

334

162

328

397

484

183

214

252

421

387

354

179

160

269

308

375

456

536

316

387

470

527

382

286

472

180

157

189

197

195

195

119

119

108

114

108

111

121

120

111

97

280

281

380

521

522

583

159

266

320

343

367

393

422

471

20%

153

186

244

337

189

331

405

491

210

250

296

431

401

362

202

173

280

313

385

474

555

321

398

485

542

396

300

493

230

178

202

201

198

197

128

129

120

125

123

120

128

131

118

110

283

284

390

530

528

590

188

281

330

351

376

403

435

485

30%

162

192

250

342

208

334

410

498

230

278

335

442

416

370

223

185

291

317

392

484

572

324

404

495

552

408

309

514

279

194

212

205

203

201

137

141

132

137

137

129

134

142

127

119

286

286

403

536

533

596

210

294

338

358

382

409

444

492

40%

171

198

254

346

222

337

416

505

246

302

370

455

432

379

244

196

303

321

398

494

586

328

412

602

564

418

319

540

324

206

223

209

206

205

149

152

143

148

150

136

140

149

134

127

288

290

416

54 1

538

602

228

303

344

364

388

416

452

500

50%

180

203

260

351

233

340

422

512

259

329

400

468

451

389

265

208

313

325

405

503

601

331

419

508

573

430

328

568

363

222

237

215

213

210

162

167

157

162

167

143

144

156

142

138

292

294

427

546

543

608

245

315

350

369

396

424

460

508

60%

188

210

265

356

246

344

429

521

275

353

433

481

468

400

286

219

324

328

412

512

616

334

425

515

583

441

335

597

396

238

255

222

220

216

177

183

175

178

186

150

149

162

151

144

296

297

443

551

549

614

262

326

357

375

402

432

468

516

70%

198

217

270

362

257

348

437

534

290

379

461

498

486

412

308

229

334

333

420

524

635

338

433

522

595

455

346

625

430

261

277

233

229

225

197

205

196

198

207

156

152

170

162

151

302

302

456

557

558

62 1

278

334

363

382

408

442

476

524

80%

210

226

278

370

270

354

449

550

306

404

491

518

509

425

329

242

346

339

431

541

656

344

444

531

609

472

356

655

459

292

307

247

242

238

229

235

224

226

235

163

157

176

168

159

310

309

469

565

566

631

303

344

370

392

418

453

485

538

F.

90%

227

242

288

382

287

364

465

577

327

431

523

552

54 1

444

352

259

362

350

448

567

683

351

459

545

633

496

372

701

495

335

345

269

260

256

295

292

280

280

286

174

162

188

179

166

322

320

490

576

582

647

327

360

384

407

434

471

503

565

Vol. 33, No. 6

E.P.

279

283

316

411

322

392

497

648

374

471

597

622

616

480

385

292

390

382

481

636

736

379

483

586

681

538

415

750

538

404

399

305

298

300

395

405

409

399

399

218

205

230

222

210

370

365

522

605

62 1

678

362

388

428

451

473

507

546

613

Residue

1.0

0.5

1.0

1.0

0.8

1.o

1.o

1.0

1.2

1.5

1.5

1.o

1.0

1.5

1.0

0.9

1.2

1.0

1.0

1.0

0.5

1.0

1.0

1.0

0.7

1.5

1.5

1.0

1.0

2.0

1.2

0.5

0.5

0.5

0.8

1.o

0.8

0.8

0.9

0.5

0.5

0.5

0.5

0.6

1.0

0.5

1.0

1.o

1.0

2.0

0.5

1.5

1.o 1.o

1.0

1.0

1.0

1.5

Lass

1.o

0.5

0

0

2.2

0

0

0

1.8

0.5

0

0

0

0

1.0

1.0

0.5

0

0

0

0

0

0

0

0

0

0.5

0

2.0

1.0

0.3

0

0

0

1.2

1.o

2.7

z.2

4.1

0.6

0.5

0

2.0

4.5

0

0

0

0

0

0

1.5

0.7

0.6

0

0

0

0

0

FIGURE1. DERIVATIONOF EQUIVALENTSMOOTH T. B. P. CURVE

and slope of the “equivalent” smooth distillation curve through the stairstep plateaus will change but little. This latter statement may need qualification in cases where mix- tures consist of only two or three pure compounds. It appears that the Podbielniak high-temperature column (7) is more powerful than the earlier packed T. 13. P. columns

of the Peters type (6). This paper will not attempt a thor- ough discussion of the factors and their relative importance, which determine the precision and effectiveness of the T. B. P. analysis. The most important factors are column length and efficiency per unit length, reflux ratio, size of batch charged, and liquid holdup capacity of the column under operating conditions. The Podbielniak column is equivalent to only

seven to fourteen equilibrium bubble

trays (2, 8), depending

upon the diameter of the standard column; however, the liquid holdup capacity of the column is very small and enables a low ratio of holdup to charge capacity to be ob- tained. As a result, at high reflux ratios and slow distillation rates relatively sharp T. B. P. fractionation may be realized. Particularly in analyses of straight-run (uncracked) naphthas

lune, 1941

INDUSTRIAL

AND

ENGINEERING

CHEMISTRY

Sample

NO.

1

2

3

4

:

7

8

9

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

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

TABLEI.

DISTILLATIONDATA(Continued)

A.

P., I.

Name

Gravity

I.B.P.

l%a

10%

Rubber solvent

77.2

30

34

100

66.6

95

103

137

?&@h&BP.

naphtha

61.2

150

166

214

Stoddard solvent

54.1

250

280

309

Naphtha

61.6

-

40

-

27

109

Naphtha

47.4

268

280

307

Kerosene

41.0

317

340

367

Gas oil

34.7

390

410

465

Naphtha

Blend

57.6

50.6

-

40

- 22

132

-40

- 10

162

Blend

45.3

-

40

0

197

Gas oil

37.6

310

340

391

Blend

38.9

240

300

351

Naphtha

42.6

240

285

330

Gasoline

62.1

32

52

142

Naphtha

Naphtha

67.7

56.3

 

32

43

121

140

178

238

Unstripped naphtha,

47.9

200

235

286

Unstripped kerosene ,

41.5

230

275

361

Unstripped gas oil

35.5

260

300

429

Gas oil

30.0

360

395

488

Unstripped naphtha

48.4

170

235

297

Unstripped kerosene

41.4

182

270

366

Unstri ped gas oil

35.5

300

305

450

Gas oiy

31.0

360

400

491

Unstri

ped kerosene

43.6

207

364

Naphtfa

Gas oil

51.4

28.6

124

170

352

251

426

Blend

52.6

68

86

155

Cracked gasoline

39.1

0

27

97

Cracked gasoline

34.5

0

25

150

Cracked naphtha

34.8 *

130

150

160

Cracked naphtha

34.4

140

160

174

Cracked naphtha

31.5

150

174

176

Polymer gasoline

58.7

15

30

86

Polymer gasoline

57.5

20

40

92

Polymer gasoline

61.7

-

-

20

20

69

Polymer gasoline

59.4

20

5

61

Polymer gasoline

61.4

25

35

80

Light naphtha

15

25

65

Light naphtha

74:5

15

25

72

Light naphtha

74.2

15

25

70

Light naphtha

77.8

0

15

62

Light naphtha

80.8

-5

5

51

Heavy naphtha,

52.1

130

210

263

Heavy naphtha

48.6

158

216

265

Kerosene

39.7

238

288

346

Gas oil

34.5

340

370

486

Aromatic extrict

14.8

346

398

484

Gas oil

32 9

412

482

565

Gasoline

63.5

0

16

99

Naphtha

55.1

104

150

228

N,apphtha

5P.9

€44

204

2%8

Naphtha

50.8

158

234

326

Naphtha

48.8

160

255

364

Kerosene

47.0

2

10

285

378

Kerosene

44.9

212

262

400

Gas oil

42.8

145

300

436

 

True Boiling Point Distillation,

F.

20%

30%

40%

50%

60%

70%

80%

90%

95%

98%

131

151

167

180

197

214

231

252

268

282

160

176

190

203

214

227

242

258

268

282

222

240

252

260

266

271

284

306

316

326

317

327

341

351

358

368

385

397

404

414

161

190

212

230

249

262

281

301

320

347

317

326

333

340

347

356

365

379

394

413

388

400

412

422

434

449

460

478

495

512

482

496

506

516

532

546

668

600

635

672

177

212

235

257

278

301

323

345

364

383

217

255

293

330

264

395

420

455

472

496

252

305

357

401

438

473

503

544

580

617

415

434

467

476

493

511

536

571

603

645

380

409

435

460

481

502

522

662

597

638

353

371

387

405

417

430

452

470

492

502

179

211

238

267

290

316

342

374

391

403

152

173

193

211

240

247

262

280

291

310

264

291

307

316

339

353

361

382

400

408

300

310

320

329

339

349

358

374

392

412

377

396

407

415

430

441

455

474

489

512

462

478

492

504

517

534

550

589

622

662

514

538

563

591

619

652

685

711

729

742

312

322

327

331

338

346

353

364

373

383

383

395

406

422

434

446

460

475

487

500

474

487

496

505

518

534

551

575

588

598

529

550

570

585

599

614

630

653

682

389

405

422

439

456

475

495

527

553

568

279

304

317

330

339

350

364

383

393

403

464

500

533

568

608

643

682

738

794

832

216

260

298

350

393

430

462

497

140

163

183

203

225

249

277

335

390

435

170

186

203

249

238

268

312

353

393

430

161

169

181

195

210

227

245

269

277

290

175

187

201

214

227

240

256

280

297

310

176

183

194

210

220

234

249

277

296

310

103

118

136

154

172

198

230

295

348

410

104

130

147

168

189

212

240

295

352

412

94

114

136

159

179

207

233

291

355

420

94

117

140

160

178

200

231

289

350

400

100

120

143

162

183

210

241

296

335

380

89

112

132

145

151

157

170

189

200

203

102

126

140

146

151

154

160

168

190

203

99

127

144

153

162

175

189

202

208

212

84

102

123

139

148

156

169

189

202

212

80

97

118

135

144

153

163

181

200

206

271

280

287

293

298

306

314

335

347

356

275

281

287

294

300

308

319

333

342

350

360

380

400

418

439

454

473

493

510

528

501

518

538

548

552

564

580

603

617

632

508

518

528

537

547

558

573

602

624

645

582

590

598

608

620

626

635

662

678

690

150

184

209

231

251

279

304

332

349

370

262

288

310

324

338

350

363

382

394

402

316

330

342

356

364

372

385

402

413

422

345

357

365

374

382

392

405

424

442

460

376

388

396

407

419

432

445

465

480

504

394

408

426

438

448

462

874

498

515

526

420

432

447

456

472

484

500

520

536

556

452

462

484

502

513

527

548

576

606

640

a Volume per cent.

797

and gasolines, the Podbielniak column may give pronounced plateaus throughout the entire distillation range if the reflux ratio is maintained relatively high. Hence in the present cor- relation work, the T. B. P. curves of the various samples are arbitrarily defined in terms of the equivalent smooth curves drawn through the plateaus, since only in this way can a practical simple correlation basis be obtained. The method of arriving at these equivalent smooth curves is illustrated in Figure 1; the derived curve is drawn, leaving on both sides of the equivalent curve approximately equal areas between the experimental and derived curves. Although this treatment was necessary in the case of a large number of T. B. P. distilla- tions, the majority were carried out with less efficient frac- tionation where the plateaus were less pronounced though present to an extent indicating effective fractionation.

Basis of Correlation

Both the A. S. T. M. and T. B. P. distillation data used were taken from routine analyses and are subject to the normal experimental errors inherent in such work. A critical survey

of the many distillations showed that the most common ap parent inaccuracy occurred in errors in temperature levels due to shifts, between analyses, in the calibrations. of' 'the thermocouples and thermometers used in the T. B. P. and A. S. T. M. distillations, respectively. This is evident from comparisons of the 50 per cent boiling point temperatures

FIGURE2.

T. B. P. 50 PER CENT TEMPERATUREus.

A. S. T. M. 50 PERCENTTEMPERATURE

798

INDUSTRIAL

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ENGINEERING

CHEMISTRY

Vol. 33, No.

6

T. B. P. (50-20 PER CENT)TEMPERATUREDIF-

FERENCE us. A. S. T. M. (50-20 PERCENT)TEMPERATCREDIF-

FIGURE3.

FERENCE

in Table I. Errors in the absolute temperature level read, however, will simply displace a distillation curve vertically and not change its shape. For this reason the relation between the two types of distillation curves is here developed in terms of comparative temperature differences for similar portions of both curves, after establishment of one absolute tempera- ture point on each curve from a correlation between the 50 per cent temperatures. Selection of the most probable values for the latter relation is made possible by the large number of analyses considered. The estimation of the A. S. T. M. distillation curve by the method here offered involves seven steps, using the graphical correlations indicated’:

or could be closely estimated. the present purpose.

This seems satisfactory for

Derivation of Relations

A. S. T. M. 50 PERCENTTENPERATURE.By the method

of correlation adopted, it was necessary to establish only one

absolute temperature point on the A. S. T. M. curve. The required relation was obtained from consideration of the mid-boiling points on the two curves, and is shown on Figure 2 where the 50 per cent A. S. T. M. temperature (cor- rected for loss) is expressed as a function of the T. B. P. 50 per cent temperature. For temperatures higher than approxi- mately 550’ F. the curve is of questionable significance, since the A. S. T. M. 50 per cent points were obtained from distilla- tions under vacuum, and extensive scattering of the points around the correlation line was obtained. For lower tempera- tures the position and slope of the line were firmly established. In the case of several samples (Table I) the differences be- tween the 50 per cent temperatures were excessive; the evi- dence indicates that these were due to errors in the measured temperature levels resulting from unnoticed variations in the base calibrations of thermometers or thermocouples. No con- sistent effect of slope of T. B. P. curve upon the above relation could be determined.

A. S. T. M. 50-20 AND 80-50

PERCENTTEMPERATURES.

In the investigation of the relative slopes of the T. B. P. and A. S. T. M. curves between the 20 and 80 per cent points, it became evident that separate treatment was necessary for the 20-50 per cent portions and the 5G80 per cent portions. The relative temperatuqe differences over the 20-50 per cent sections were found to depend upon the slopes of the front- end “tail” of the T. B. P. curves. The temperature differ- ence for the 10-20 per cent portion proved to be a satisfactory correlating variable. Likewise, for the 50-80 per cent por- tions, the relative temperature differences are dependent upon the slope of the higher boiling (80-98 per cent) part of the T. B. P. curve. Figures 3 and 4 show the average correlations

T.B. P. Temp

A.

S. T. M. Temp

Figure No.

50%

50-20’%0

50%

50-20%

2

3

EER

4

5

lO-l%

10-initial

B

P.

G

98-5070

End pojnt-50%

7

98-90%

End point-90%

8

Thus after the 50 per cent vaporization tem- perature for the A. S. T. M. curve has been estimated, the temperatures corresponding to other percentages are determined as differ- ences from this fixed base point. The proce- dure &ems laborious, but in case it is not necessary that all points on the A. S. T. M. curve be established (for example, when only the initial boiling point and end point are required) the procedure may be

shortened. As stated previously, the T. B. P. data used were taken from routine analyses carried out over an extended period on various ex- perimental projects. Inmost of those analy- ses it was not practical to carry the distilla- tions to an unusually small amount of still bottoms. Most of the distillations, how- ever, were carried sufficiently far so that the 98 per cent distilled points were attained

1 More usable oopies of the oorrelation graphs may be obtained by writing to the Stone & Webster Engineer- ing Corporation.

,

100

5

sz

s

2 50

- m

I

c

v1

U

0

TRUE

BOILING POINT (80%-50%),”F

0

FIGURE4.

T.

B.

P.

(80-50

PER CENT) TEMPERATUREDIFFERENCEvs.

A. s. T. M. (80-50 PERCENT)TEMPERATUREDIFF~RENCE

June, 1941

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deviation of the experimental points from the correlation is

very satisfactory

since errors of this magnitude may be obtained in both ex-

The true error of the relation

is probably less.

mining the trends of the lines beyond the ranges indicated. One would suspect that the relation would depend, in addi- tion, upon the proportion of the total T. B. P. 98-80 per cent temperature difference obtained in the 90-80 per cent inter- val. Hence the present correlation should be applied with caution to abnormal blends whose T. B. P. distillation curves are relatively flat in the 80-90 per cent portion, with very long tails in the 95-98 per cent part; the correlation presented is based upon products obtained by normal fractionation processes. As Figure 7 indicates, the increasing effect of superheating at the A. S. T. M. end point, with decreasing end point of samples, in giving fictitiously high A. S. T. M. end

points was clearly established statistically. This was par- ticularly apparent for the available samples having end points in the range 200-300° F., where the A. S. T.