cumene to phenol

A Report on

Production of Phenol from 99.9% pure Cumene from Naptha Cracker Production of 99.9% pure Bisphenol A from 99.9% pure Phenol February-14-2015

Major Project Report Submitted by Virender Pratap Singh Department of Chemical Engineering IIT Roorkee

Index 1. Material and Energy Balance 1.1 Material Balance 1.2 Energy Balance 2. Environmental Protection & Energy Conservation 2.1 Air Pollution 2.2 Liquid Effluents 2.3 Solids disposal 2.4 Noise Pollution 2.5 Energy conservation 3. Organizational Structure and Manpower Requirement 3.1 Organizational Principles and Basics 3.2 Hierarchy 3.3 Manpower Requirement 4. SITE SELECTION & PROJECT LAYOUT 4.1 Plant Location 4.2 Plant Layout

1|Page

1. MATERIAL AND ENERGY BALANCE 1.1

Material Balance

BASIS: 24133 kg/hr production of phenol 1.1.1 Overall reactions: 1. Oxidation of Cumene: NaOH C6H5CH(CH3)2

+

(120)

O2

C6H5C (CH3)2OOH

(32)

(152)

2. Decomposition of Cumene hydroperoxide: C6H5C (CH3)2OOH

+

H2S04

C6H5OH

(152)

+

(94)

1.1.2 Molecular weights of components: Cumene (Isopropyl benzene) = 120 kg moles Cumene Hydroperoxide

= 152 kg moles

Oxygen

= 32 kg moles

Phenol

= 94 kg moles

Acetone

= 58 kg moles

Mass of inlet of Cumene and oxygen

= 120+32=152 kg moles

Mass of outlet of phenol and acetone INLET

= 94+52= 152 kg moles

=

1.1.3 Feed: Cumene = 1650 kg (For 1000 kg of Phenol) Required oxygen = 440 kg 1 kg of air contains 0.23 kg of O2 X kg of air contains 440 kg of O2 Amount of air supplied = 1913 kg of air 25% excess air supplied = 478 kg of air Actual amount of air supplied = 2319 kg of air 1.1.4 Balances:

2|Page

OUTLET

CH3COCH3 (58)

OXIDIZER: COMPONENTS

INLET kg/hr

OUTLET kg/hr

Cumene

39552.975

10020.087

Air

57315.8565

---

Cumene hydroperoxide

----

40080.348

Off gases

----

46768.3965

Total

96868.8315

96868.8315

COMPONENTS

INLET kg/hr

OUTLET kg/hr

Cumene hydroperoxide

40080.348

10022.48415

Cumene

10020.087

---

Cleavage

---

40089.9366

H2SO4

11.98575

---

Total

50112.42075

50112.42075

COMPONENTS

INLET kg/hr

OUTLET kg/hr

Cumene hydroperoxide

40089.9366

10022.48415

Carryover Cleavage

---

1002.0087

Cleavage

10022.48415

39087.9279

Total

50112.42075

50112.42075

INLET kg/hr

OUTLET kg/hr

ACIDIFIER:

SEPARATOR:

WASH TOWER: COMPONENTS

3|Page

Cleavage

39087.9279

---

Water

575.316

---

Acid free Cleavage

---

38968.0704

Acidified wash water

---

695.1735

Total

39663.2439

39663.2439

ACETONE COLUMN: COMPONENTS

INLET kg/hr

OUTLET kg/hr

OVERHEAD BOTTOM

Cleavage

38968.0704

---

---

Acetone

---

11956.9842

---

Carryover cleavage

---

119.8575

---

Carryover acetone in residue

---

---

119.8575

Residue

---

---

26771.3712

Total

38968.0704

12076.8417

26891.2287

COMPONENTS

INLET kg/hr

OUTLET kg/hr

OVERHEAD BOTTOM

Feed

26891.2287

---

---

Cumene

---

1948.88295

---

Carryover acetone in Cumene

---

119.8575

---

Residue

---

---

24822.48825

Total

26891.2287

2068.74045

24822.48825

CUMENE COLUMN:

α - METHYL STYRENE COLUMN:

4|Page

COMPONENTS

INLET kg/hr

OUTLET kg/hr

OVERHEAD BOTTOM

Feed

24822.48825

---

---

α - methyl styrene

---

546.5502

---

Residue

---

---

24275.93805

Total

24822.48825

546.5502

24275.93805

COMPONENTS

INLET kg/hr

OUTLET kg/hr

OVERHEAD BOTTOM

Feed

24275.93805

---

---

Phenol

---

24041.01735

---

Carryover acetophenone

---

91.0917

---

Acetophenone

---

---

119.8575

Total

24275.93805

24132.10905

119.8575

PHENOL COLUMN:

The amount product phenol = 24133 kg/hr Purity of the product phenol = 99.9%

1.2

Energy Balance

5|Page

OXIDIZER: A) Inlet heat@ 70°C: 1. Cumene @ 30°C mass 1

39552.975

Cp1

0.415

ΔT1

5

Q1

kg kcal/kg °C °C

82072.42313

Kcal

343473.0908

KJ

57315.8565

kg

2. Air @ 30°C mass 2 Cp2

1.005

ΔT2

5

Q2

KJ/kg °C °C

288012.1789

KJ

40080.348

kg

3. Total heat inlet Q = Q 1+ Q 2 Q = 631485.2697 KJ B) Outlet heat@ 110°C: 1. Cumene Hydroperoxide @ 110°C mass 1 Cp1

0.45

ΔT1

85

Q1

2. Cumene @ 110°C

6|Page

kcal/kg °C °C

1533073.311

Kcal

6415911.807

KJ

mass 2

10020.087

Cp2

0.455

ΔT2

85

Q2

Kg kcal/kg °C °C

387526.8647

Kcal

1621799.929

KJ

3. Off gases @ 110°C a) Oxygen mass 3

2636.865

Cp3

0.936

ΔT3

25

Q3

61702.641

Kg KJ/kg °C °C KJ

b) Nitrogen mass 4

44131.5315

Cp4

1.035

ΔT4

25

Q4

1141903.378

Kg KJ/kg °C °C KJ

4. Total heat outlet Q= Q1+ Q2+ Q3+ Q4 Q = 1044923.774 KJ Heat of reaction of Cumene Hydroperoxide = 736 KJ/kg For 38171.76kg of Cumene Hydroperoxide

COMPONENTS

7|Page

= 29499136.13

INLET HEAT KJ

OUTLET HEAT KJ

Cumene

343473.0908

1621799.929

Air

288012.1789

---

Cumene hydroperoxide

29499136.13

---

Cumene hydroperoxide

---

6415911.807

Off gases

---

1203606.019

Heat removed by water

---

19894575

Total

30130621.4

29135892.75

COOLER: A) Inlet heat @ 110°C: Heat taken by Cumene Hydroperoxide

6415911.807

KJ

Heat taken by Cumene

1621799.929

KJ

Total Heat

8037711.735

KJ

B) Outlet heat @70°C: 1. Cumene hydroperoxide @ 70°C: mass 1

40080.348

Cp1

0.45

ΔT1

45

Q1

811627.047 3396659.192

2. Cumene @ 70°C:

8|Page

kg kcal/kg °C °C Kcal KJ

mass 2

10020.087

Cp2

0.435

ΔT2

45

Q2

196143.203 820859.3047

3.

kg kcal/kg °C °C Kcal KJ

Total heat outlet Q= Q1+ Q2 Q = 4217518.496

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Cumene hydroperoxide

6415911.807

3396659.192

Cumene

1621799.929

820859.3047

Heat removed by water

---

3638279

Total

8037711.735

8027810

ACIDIFIER: A) Inlet heat @ 70°C: Heat taken by Cumene Hydroperoxide Heat taken by Cumene Total Heat

3396659.192 820859.3047 4217518.496

1. H2SO4 @ 30°C:

mass 2 Cp2

1.44

ΔT2

45

Q2

9|Page

11.98575

776.6766

kg KJ/kg °C °C KJ

2. Total heat inlet Q = Q1+Q2 = 4218295.173KJ B) Outlet heat @ 80°C: 1. Mass of cleavage = 40089.9366 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24856.04835

2.29

Acetone

12426.8256

1.481

Cumene

2004.0174

1.842

α - methyl styrene

563.33025

1.406

Acetophenone

244.5093

1.97

Q1=((24856.048×2.29)+( 12426.8256*1.481)+( 2004.0174×1.842)+( 536.33025×1.406)+( 244.5093×1.97)) ×(80-25) Q1= 4415928.283 KJ 2. Cumene hydroperoxide@ 80°C: mass 2

10022.48415

Cp2

0.45

ΔT2

55

Q2

248056.4827 1038116.38

3. Total heat outlet Q = Q1+Q2 = 5454044.663 KJ Heat of reaction of cleavage = 2983 KJ/kg For 38180.9 kg of cleavage =113893624.7

10 | P a g e

kg kcal/kg °C °C Kcal KJ

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Cumene Hydroperoxide

3396659.192

1038116.38

Cumene

820859.3047

---

H2SO4

776.6766

---

Heat of reaction of cleavage

113893624.7

---

Cleavage

---

4415928.283

Heat removed by water

---

112716720.4

Total

118111919.9

118170765.1

SEPARATOR: A) Inlet heat @80°C: Heat in Cumene Hydroperoxide

1038116.38

Heat in Cumene

4415928.283

Total

5454044.663

B) Outlet heat @80°C: Heat in Cumene Hydroperoxide

1038116.38

Heat in cleavage

4415928.283

Total heat outlet

5454044.663

WASH TOWER: A) Inlet heat @80°C: 1. Mass of Cleavage =39087.9279 kg SPECFIC HEAT KJ/Kg°C 2.29

COMPONENTS

MASS kg

Phenol

24235.1865

Acetone

12117.59325

1.481

Cumene

1953.67725

1.842

α - methyl styrene

546.5502

1.406

Acetophenone

234.9207

1.97

11 | P a g e

Q1= 4305105.725 KJ 2. Water @ 30°C

mass 2

575.316

Cp2

4.18

ΔT2

5

Q2

12024.1044

kg KJ/kg °C °C KJ

3. Total heat inlet Q = Q1+Q2 = 4317129.829 B) Outlet heat @75°C: 1. Acid free cleavage = 38969.074 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24158.4777

2.29

Acetone

12076.8417

1.462

Cumene

1948.88295

1.821

α - methyl styrene

546.5502

1.367

Acetophenone

234.9207

1.97

Q1=4275595.914 KJ 2. Acidified wash water @ 40°C mass 2

575.316

Cp2

4.18

ΔT2

15

Q2

36072.3132

3. Heat taken by carryover cleavage Q3=5201.9KJ

12 | P a g e

kg KJ/kg °C °C KJ

4. Total heat outlet Q= Q1+Q2+ Q3= 4316869.727 KJ COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Cleavage

4305105.725

---

Water

12024.1044

---

Acid free cleavage

---

4275595.514

Acidified wash water

---

36072.3132

Carryover cleavage

---

5201.9

Total

4317129.829

4316869.727

HEATER: A) Inlet heat @75°C: Cleavage Mass of cleavage = 38968.0704 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24158.4777

2.29

Acetone

12076.8417

1.462

Cumene

1948.88295

1.821

α - methyl styrene

546.5502

1.367

Acetophenone

234.9207

1.97

Q = 4275595.514 KJ B) Outlet heat @90°C: Mass of cleavage = 38968.0704 COMPONENTS

MASS kg

Phenol

24158.4777

2.29

Acetone

12076.8417

1.509

13 | P a g e

SPECFIC HEAT KJ/Kg°C

Cumene

1948.88295

1.863

α - methyl styrene

546.5502

1.445

Acetophenone

234.9207

1.97

Q = 4313660.77 KJ

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Cleavage

4275595.514

4313660.77

Heat added by steam

36252.62

Total

4311848.134

--4313660.77

ACETONE COLUMN: A) Inlet heat @90°C: Mass of cleavage =38689.0704 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24158.4777

2.29

Acetone

12076.8417

1.509

Cumene

1948.88295

1.863

α - methyl styrene

546.5502

1.445

Acetophenone

234.9207

1.97

Q = 5097962.728 KJ B) Outlet heat: 1. Acetone vapours @ 56°C Mass 1

14 | P a g e

11956.9842

λ1

212.3

Q1

2538467.746

kg KJ/kg °C KJ

2. Cleavage vapours @ 56°C Mass 2

119.8575

λ2

109.96

Q2

13179.5307

kg KJ/kg °C KJ

3. Total heat outlet as vapour = 2551647.276 4. Bottom residue @90°C Mass of residue= 2799.8712 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24086.5632

2.32

Cumene

1948.88295

1.863

α - methyl styrene

546.5502

1.445

Acetophenone

234.9207

1.97

Q3= 2126745.403KJ

5. Carryover acetone @90°C mass 4 Cp4

1.509

ΔT4

65

Q4

6. Total heat outlet Q = Q1+Q2+ Q3+ Q4 Q =4690148.902 KJ

15 | P a g e

119.8575

11756.22289

kg KJ/kg °C °C KJ

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Cleavage

5097962.728

Vapour acetone

---

2538467.746

Vapour cleavage

---

13179.5307

Bottom residue

---

2126745.403

Carryover acetone in residue

---

11756.22289

Total

5097962.728

5097954

---

OVERHEAD ACETONE CONDENSER: A) Inlet heat @ 56°C: 1. Acetone vapours @ 56°C Mass 1

11956.9842

kg

λ1

212.3

KJ/kg °C

Q1

2538467.746

KJ

119.8575

kg

2. Cleavage vapours @ 56°C Mass 2 λ2

109.96

KJ/kg °C

Q2

13179.5307

KJ

11956.9842

kg

3. Total heat inlet as vapour Q = Q1+Q2 Q= 2551647.276 B) Outlet heat@50°C: 1. Acetone mass1 Cp1

1.397

ΔT1

25

Q1

16 | P a g e

417597.6732

KJ/kg °C °C KJ

2. Heat produced by Cleavage Q2 = 4837.75 KJ 3. Total heat outlet Q = Q1+Q2 Q = 422435.4232 KJ

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Vapour acetone

2538467.746

---

Vapour cleavage

13179.5307

---

Heat removed by water

---

2027590.4

Condensed acetone

---

417597.6732

Condensed cleavage

---

4837.75

Total

2551647.276

2541652

HEATER: A) Inlet heat @90°C: 1. Mass of residue= 2799.8712 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24086.5632

2.32

Cumene

1948.88295

1.863

α - methyl styrene

546.5502

1.445

Acetophenone

234.9207

1.97

Q1 = 2126745.403 KJ 2. Acetone mass2 Cp2

1.509

ΔT2

65

Q2

17 | P a g e

119.8575

11756.22289

kg KJ/kg °C °C KJ

3. Total heat inlet Q = Q1+Q2 Q =2138501.626 KJ B) Outlet heat @95°C: 1. Mass of residue= 2799..8712 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24086.5632

2.32

Cumene

1948.88295

1.863

α - methyl styrene

546.5502

1.445

Acetophenone

234.9207

1.97

Q1=2126745.403 KJ 2. Acetone mass2

119.8575

Cp2

1.51

ΔT2

70

Q2

12668.93775

kg KJ/kg °C °C KJ

3. Total heat outlet Q = Q1+Q2 =2139414.341 KJ COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Residue

2126745.403

2126745.403

Carryover acetone

11756.22289

12668.93775

Heat added by steam

869.25

Total

2139370.876

CUMENE COLUMN: A) Inlet heat @95°C: 1. Mass of feed= 2799.8712 kg

18 | P a g e

--2139414.341

COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24086.5632

2.32

Cumene

1948.88295

1.863

α - methyl styrene

546.5502

1.445

Acetophenone

234.9207

1.97

Q1=4253490.806 KJ 2. Acetone mass2

119.8575

Cp2

1.51

ΔT2

70

Q2

kg KJ/kg °C °C

12668.93775

KJ

1948.88295

kg

3. Total heat inlet Q = Q1+Q2 = 4266159.744 KJ B) Outlet heat: 1. Cumene vapours @ 90°C

Mass 1 λ1

343.9

KJ/kg °C

Q1

670220.8465

KJ

119.8575

kg

2. Acetone vapours @ 90°C Mass 2

19 | P a g e

λ2

212.3

Q2

25445.74725

KJ/kg °C KJ

3. Residue @ 95°C Mass = 24822.48225 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24086.5632

Cumene

1948.88295

1.863

α - methyl styrene

546.5502

1.445

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Feed

4253490.806

---

Vapour Cumene

---

670220.8465

Vapour acetone

---

25445.74725

Residue

---

4253490.806

Carryover acetone in feed

12668.93775

---

Total

4713483

4949157.4

2.32

Q3 = 4253490.806 KJ 4. Total heat outlet Q = Q1+Q2+Q3=4949157.4 KJ

CUMENE VAPOUR CONDENSER: A) Inlet heat: 1. Cumene vapours @ 90°C Mass 1

20 | P a g e

1948.88295

λ1

343.9

Q1

670220.8465

kg KJ/kg °C KJ

2. Acetone vapours @ 90°C Mass 2

119.8575

kg

λ2

212.3

KJ/kg °C

Q2

25445.74725

KJ

1948.88295

kg

3. Total heat inlet Q Q1+Q2 = 695666.5938 KJ B) Outlet heat@80°C: 1. Cumene mass1 Cp1

1.842

ΔT1

55

Q1

KJ/kg °C °C

197441.3317

KJ

119.8575

kg

2. Acetone mass1 Cp1

1.51

ΔT1

55

Q1

9954.165375

KJ/kg °C °C KJ

3. Total heat outlet Q = Q1+Q2 = 207395.497 KJ COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Vapour Cumene

670220.8465

---

Vapour acetone

25445.74725

---

Heat removed by water

---

465020.1

Condensed Cumene

---

197441.3317

Condensed acetone

---

9954.165375

21 | P a g e

Total

695666.5938

695670.5

Total

662539.6131

662539.621

HEATER: A) Inlet heat @ 95°C: 1. Mass = 24822.48825 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24086.5632

α - methyl styrene

546.5502

1.445

Acetophenone

234.9207

1.97

2.32

Q = 3999336.981 KJ B) Outlet heat @ 110°C: 1. Mass = 24822.48825 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24086.5632

α - methyl styrene

546.5502

1.445

Acetophenone

234.9207

1.97

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Residue

3999336.981

4856337.763

Heat added by steam

816191

Total

4815527.981

2.32

Q=4856337.763 KJ

22 | P a g e

--4856337.763

α - METHYL STYRENE COLUMN: A) Inlet heat @ 110°C: 1.

Mass 24822.48825 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24086.5632

α - methyl styrene

546.5502

1.523

Acetophenone

234.9207

1.97

2.32

Q=4859961.39 KJ B) Outlet heat: 1. α - methyl styrene vapours @ 100°C Mass 1

546.5502

λ1

449.1

Q1

245455.6948

kg KJ/kg °C KJ

2. Residue @110°C Mass = 24275.93805Kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24041.01735

Acetophenone

234.9207

1.97

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Residue

4859961.39

Vapour α - methyl styrene

---

245455.6948

Bottom residue

---

4780226.093

Total

4859961.39

4859960

2.32

Q2 = 4780229.093 KJ 3. Total heat outlet Q = Q1+Q2 = 5025681.787 KJ

23 | P a g e

---

α - METHYL STYRENE CONDENSER: A) Inlet heat: 1. α - methyl styrene vapours @ 100°C Mass 1

546.5502

kg

λ1

449.1

KJ/kg °C

Q1

245455.6948

KJ

546.5502

kg

B) Outlet heat: 1. α - methyl styrene condensed @ 95°C mass 1 Cp1

1.445

ΔT1

70

Q1

55283.55273

KJ/kg °C °C KJ

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Vapour α - methyl styrene

245455.6948

Heat removed by water

---

181116.3

Condensed α - methyl styrene

---

55283.55273

Total

245455.6948

236399.8527

---

HEATER: A) Inlet @110°C 1. Mass =24275.93805 kg COMPONENTS

MASS kg

Phenol

24041.01735

Acetophenone

234.9207

24 | P a g e

SPECFIC HEAT KJ/Kg°C 2.32 1.97

Q=4780226.093 KJ

B) Outlet @130°C 1. Mass =24275.93805 kg COMPONENTS

MASS kg

SPECFIC HEAT KJ/Kg°C

Phenol

24041.01735

Acetophenone

234.9207

1.97

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Residue

4780226.093

5904985.173

Heat added by steam

1071199

Total

5851425.093

2.32

Q=5904985.195KJ

--5904985.173

PHENOL COLUMN: A) Inlet @130°C 1. Mass =24275.93805 kg COMPONENTS

MASS kg

Phenol

24041.01735

Acetophenone

234.9207

SPECFIC HEAT KJ/Kg°C 2.32 1.97

Q=5904985.173 KJ B) Outlet heat 1. Phenol vapours @ 120°C Mass 1

25 | P a g e

24041.01735

λ1

296.7

Q1

7132969.848

kg KJ/kg °C KJ

2. Acetophenone vapours @ 120°C Mass 2

91.0917

kg

λ2

116.1

KJ/kg °C

Q2

10575.74637

KJ

3. Bottom acetophenone @130°C mass 3

119.8575

kg

Cp3

1.97

KJ/kg °C

ΔT3

105

°C

Q3

24792.52388

KJ

4. Total heat outlet Q= Q1+Q2+ Q3= 7168338.118 COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Feed

7168338.1

Vapour phenol

---

7132969.848

Vapour Acetophenone

---

10575.74637

Acetophenone

---

24792.52388

Total

7168338.1

7168338.118

---

PHENOL VAPOUR CONDENSER: A) Inlet heat 1. Phenol vapours @ 120°C Mass 1 λ1

296.7

Q1

7132969.848

2. Acetophenone vapours @ 120°C

26 | P a g e

24041.01735

kg KJ/kg °C KJ

Mass 2

91.0917

λ2

116.1

Q2

10575.74637

kg KJ/kg °C KJ

3. Total heat inlet Q= Q1+Q2=7143545.594 KJ B) Outlet heat@ 100°C 1. Mass = 24132.10905 kg COMPONENTS

MASS kg

Phenol

24041.01735

Acetophenone

91.0917

SPECFIC HEAT KJ/Kg°C 2.32 1.97

Q=4196595.818 KJ

COMPONENTS

INLET HEAT KJ

OUTLET HEAT KJ

Vapour phenol

7132969.848

---

Vapour Acetophenone

10575.74637

---

Heat removed by water

---

2806618

Condensed phenol & acetophenone

---

4196595.818

Total

7003213

7003213.818

27 | P a g e

2. Environmental Protection & Energy conservation 2.1 AIR POLLUTION In this section, air emissions are characterized by location, effective emission heights, and emission factors for criteria pollutants and selected pollutants; the hazard potential of each pollutant is quantified, and the affected population is determined; the national and state emission burdens are calculated; and the growth factor of the industry’s emissions is determined. The data in this section were obtained through industry cooperation. SELECTED POLLUTANTS Compounds identified as potential emissions from the manufacture of acetone and phenol from cumene are listed in Table 12. A sampling program was undertaken to quantify these compounds plus others which may not previously have been known to be present. TABLE 12. SUSPECTED EMISSIONS FROM ACETONE AND PHENOL MANUFACTURE FROM CUMENE PRIOR TO SAMPLING Acetaldehyde Acetic acid Acetone α-Hydroxyacetone Diacetone alcohol Acetophenone Benzene Ethylbenzene n-Propylbenzene Methyl isobutyl carbinol Cumene Cumene hydroperoxide Dicumyl peroxide 1,1,2, 2—Tetramethyl—l,2—diphenylethane Formaldehyde Formic acid 2-Methylbenzofuran Methylgioxal Heavy tars 2, 6—Dimethyl-2, 5—heptadiene—4-one l-Hydroxyethyl methyl ketone Methyl isobutyl ketone Lactic acid Methanol α-Methylstyrene Dimers of α-methylstyrene 2-Methyl-3, 4-pentanediol

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4-Hydroxy-4-methyl- 2-pentanone Phenol 2,4,6-Tris (2-phenyl-2-propyl)phenol Toluene 2-Phenyl-2- (4-hydroxyphenyl) propane TABLE 13. CHARACTERISTICS OF EMISSIONS IDENTIFIED DURING SAMPLING OR REPORTED FROM ACETONE AND PHENOL PLANTS USING CUMENE PEROXIDATION MATERIAL EMITTED Acetaldehyde Acetone Acetophenone Benzene Cumene Ethyl benzene Formaldehyde α methyl styrene Naphthalene Phenol

HEALTH EFFECTS Local irritant; central nervous system narcotic Skin irritant, narcotic in high concentrations Narcotic in high concentrations Carcinogen Narcotic ; toxic Skin and mucous membrane irritant Irritant ; toxic Toxic Moderate irritant Toxic & irritant

TABLE 14. EMISSION SOURCES BY PROCESS TYPE AT A PLANT MANUFACTURING ACETONE AND PHENOL FROM CUMENE Process technology Allied

Hercules

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Emission source Cumene peroxidation. Cumene hydroperoxide concentration vent. Separation column vent. Acetone concentration column vent. Cumene column vent. α Methylstyrene column vent. Refined α-methylstyrene column vent. Phenol column vent. Acetophenone column vent. Cumene tank vent. Acetone tank vent. Catalyst tank vent. Acetone transport loading vent. α-Methylstyrene transport loading vent Phenol transport loading vent. Acetophenone transport loading vent. Acetophenone transport loading vent. Cumene peroxidation vent. Cumene hydroperoxide wash vent. Cumene hydroperoxide concentration vent.

Vent of cuxnene hydroperoxide cleavage and product wash operations combined. Separation column vent. Acetone column vent. Separation column vent. Dewatering column vent Hydrogenation column vent Acetone tank vent α-Methylstyrene tank vent Phenol tank vent Buffer tank vent

TABLE 15. EMISSION SOURCES AT A REPRESENTATIVE PLANT MANUFACTURING ACETONE AND PHENOL FROM CUMENE 1. Cumene Peroxidation Vent The cumene feed is contacted with air in a reaction vessel to peroxidize the cumene. Air is continuously introduced and removed. The off—gas stream carries vaporized hydrocarbons and some volatile trace elements. Cumene is recovered from the spent gas for recycle by condensation. The emission control equipment is the last piece of equipment before the gas is emitted to the atmosphere. That is, any prior equipment is process equipment, and the control of any material released to the atmosphere is performed by the last piece of equipment prior to release. For example, in the Allied process the emission control equipment is the carbon bed system, and in the Hercules process it is the refrigerated condenser, unless another piece of equipment is added on. 2. Cleavage Section Vents, Combined The composite emission factors, Table 18, are determined by aggregation of the emission factors available from sampling and industry communication. These emission factors combine values for the cumene hydroperoxide concentration vent (Allied process technology) and the cumene hydroperoxide wash vent, the cumene hydroperoxide concentration vent, and the combined cunene hydrøperoxide cleavage and product wash vent (Hercules process technology). TABLE 18. AVERAGE EMISSION FACTORS FOR THE CLEAVAGE SECTION Material emitted Total nonmethane hydrocarbon Acetone Acetophenone Benzene 2—Butanone 0.0000018 2—Butenal t—Butylbenzene Cumene

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g/kg phenol produced 0.17 0.0000060 0.0000044 0.000031 0.0000018 0.000000085 0.000023 0.14

Ethylbenzene Formaldehyde 2—Hydroxy-2—phenylpropane Isopentanal

0.0000050