Petroleum Assignment - UOP Q-Max Cumene Process (FULL)

UNIVERSITY MALAYSIA SABAH

SCHOOL OF ENGINEERING & INFORMATION TECHNOLOGY

HK03 CHEMICAL ENGINEERING PROGRAMME

SEMESTER II, 2012 / 2013

KC41803 PETROLEUM PROCESSING

GROUP ASSIGNMENT TITLE:

UOP Q-MAX CUMENE PROCESS

GROUP MEMBERS:

KENNY THEN SOON HUNG (BK09110098)

LEE CHEE HOE (BK09110001)

DATE OF SUBMISSION:

29TH MAY 2013

LECTURER:

ASSOC. PROF. IR. OTHMAN BIN ABDUL HAMID

THE PROJECT: UOP Q-MAX CUMENE PRODUCTION PROCESS

KC41803 PETROLEUM PROCESSING: GROUP ASSIGNMENT

TABLE OF CONTENTS:

1.0 HISTORY ON PETROLEUM REFINING ..................................................... 1

1.1 The Malaysian Oil And Gas Industry: An Overview ......................................... 3

1.2 Flow Diagram of Typical Refinery ............................................................... 10

1.3 Introduction On Cumene ........................................................................... 12

1.4 Cumene Production ................................................................................... 15

1.5 Cumene Properties .................................................................................... 16

1.6 Cumene Process ........................................................................................ 19

1.8 Cumene Chemical Properties ...................................................................... 21

1.9 Uses Of Cumene ....................................................................................... 24

1.10 Description On Q-Max Process .................................................................. 25

2.0 REFINERY BALANCE ............................................................................. 27

2.1 Introduction .............................................................................................. 27

2.2 The Abu Dhabi Oil Refining Company (Takreer) .......................................... 28

2.3 Refinery Installations ................................................................................. 32

2.3.1 Refinery Units ..................................................................................... 33

2.3.2 Utilities, Off-sites, Terminal & ADR Technology ..................................... 36

2.4 Mass Balance Based 400,000 BPD of Middle East Heavy Crude ..................... 40

2.4.1 Mass Balance by Assumed Proportion of Refining Products is Double ...... 41

2.4.2 Mass Balance by Fraction Method ......................................................... 44

2.4.3 Mass Balance based on Total Production from while Middle East Countries

.................................................................................................................. 46

2.5 Conclusion ................................................................................................ 51

3.0 GROUP PROJECT ................................................................................... 53

3.1 Introduction To Cumene Production ........................................................... 53

3.1.1 Cumene Project Definition .................................................................... 53

3.1.2 Cumene Manufacturing Routes ............................................................. 55

3.1.3 General Overall Material Balance for Cumene Process ............................ 58

3.1.4 Physical Properties .............................................................................. 59

3.2 Cumene Process ........................................................................................ 60



3.3.1 Technical Description ........................................................................... 61

3.2.1 Cumene Chemical Properties ................................................................ 62

3.3 Chemical Reaction Network ........................................................................ 64

3.4 Various Processes of Manufacture .............................................................. 67

3.4.1 UOP Cumene Process .......................................................................... 67

3.4.2 Badger Cumene Process ...................................................................... 71

3.4.3 MONSANTO LUMMUS CREST Cumene Process ................................... 74

3.4.4 CDTECH & ABB Lummus Global ............................................................ 75

3.4.5 Q-MAX Process .................................................................................... 82

3.5 Description On Q-Max Process ................................................................... 85

3.6 Description On Process Flow ...................................................................... 87

3.7 Process Chemistry Chemical Reactions........................................................ 89

3.7.1 Transalkylation Of DIPB ................................................................... 91

3.7.2 Side Reactions .................................................................................... 92

3.8 Process Flow Diagram (PFD) .................................................................. 94

3.9 Description ............................................................................................... 97

3.10 Cumene Plant Section .............................................................................. 98

3.10.1 Storage and pumping section ............................................................. 98

3.10.2 Preheating and vaporization section .................................................... 98

3.10.3 Reactor section ................................................................................. 99

3.10.4 Separation and purification section ..................................................... 99

3.11 Current Industrial Cumene Production Process: UOP Process ................... 100

3.12 UOP Process Description For Cumene Production .................................... 101

3.13 Description Of Process Units .................................................................. 103

3.13.1 V-201 Vaporizer ............................................................................... 104

3.13.2 R-201 Reactor ................................................................................. 104

3.13.3 S-201 Separator .............................................................................. 104

3.13.4 T-201 Distillation Tower No. 1 .......................................................... 104

3.13.5 T-202 Distillation Tower No. 2 .......................................................... 104

3.14 Description Of Process Streams .............................................................. 105

3.14.1 Stream 1 ......................................................................................... 105

3.14.2 Stream 2 ......................................................................................... 105

3.14.3 Stream 3 ......................................................................................... 105



3.14.4 Stream 4 ......................................................................................... 105

3.14.5 Stream 5 ......................................................................................... 105

3.14.6 Stream 6 ......................................................................................... 105

3.14.7 Stream 7 ......................................................................................... 106

3.14.8 Stream 8 ......................................................................................... 106

3.14.9 Stream 9 ......................................................................................... 106

3.14.10 Stream 10 ..................................................................................... 106

3.15 Reaction Mechanism And Kinetics Of Cumene Production ......................... 107

4.0 CAPACITY CALCULATION ................................................................... 108

4.1 Mass Balance .......................................................................................... 108

4.1.1 Introduction to Mass Balance ............................................................. 108

4.1.2 Material Balance of Major Equipment - Reactor ................................... 111

4.1.3 Material Balance of Propane Column ................................................... 117

4.1.4 Material Balance of Minor Equipment - Benzene Column ...................... 118

4.1.5 Material Balance of Minor Equipment Cumene Column ...................... 121

4.2 Heat Balance .......................................................................................... 124

4.2.1 Introduction to Heat Balance .............................................................. 124

4.2.2 Heat Balance for Major Equipment - Reactor ....................................... 128

4.2.3 Heat Balance for Propane Column ...................................................... 138

4.2.4 Heat Balance for Minor Equipment - Benzene Column .......................... 144

4.2.5 Heat Balance for Minor Equipment - Cumene Column ......................... 149

4.2.6 Product Yield ..................................................................................... 154

4.3 Flow Summary for Cumene Production at Design Conditions ...................... 157

4.4 Flow Summary for Utility Streams ............................................................ 160

4.4 Equipment Summary with Capacity for Cumene Producition Process ........... 161

5.0 BEHAVIOUR OF CATALYSTS/SOLVENTS............................................. 164

5.1 Feedstock Considerations ........................................................................ 164

5.1.1 Impact Of Feedstock Contaminants On Cumene Purity ..................... 164

5.1.2 Impact of Catalyst Poisons On Catalyst Performance ........................ 168

5.2 Process Performance ............................................................................... 170



5.3 Production Of Cumene Using Zeolite Catalysts .......................................... 172

5.3.1 Unocals technology is based on a conventional fixed-bed system ......... 172

5.3.2 The second zeolite process, which was developed by CR&L ................. 172

5.4 Disadvantages Of Using Solid Phosphoric Acid (SPA) Process ..................... 173

5.5 Disadvantages of Using Aluminum Chloride As Catalyst ............................. 173

5.6 Catalysts in Cumene Production Process ................................................... 174

5.7 Catalysts And Reactions ........................................................................... 176

5.8 Cumene Process And Catalysts ................................................................. 179

5.8.1 SPA Catalyst...................................................................................... 180

5.8.2 AlCl3 and Hydrogen Chloride Catalyst .................................................. 181

5.8.3 Zeolite Catalysts ................................................................................ 182

5.9 Future Technology Trends ....................................................................... 194

5.9.1 Catalysts. .......................................................................................... 194

6.0 PROCESS AND INSTRUMENTATION DIAGRAM .................................. 196

6.1 Introduction To P&ID .............................................................................. 196

6.2 P&ID Diagram ......................................................................................... 197

6.2.1 Symbols and layout ........................................................................... 198

6.2.2 List Of Pid Items ................................................................................ 199

6.2.3 Basic symbols.................................................................................... 200

6.3 Introduction to Valve ............................................................................... 204

6.3.1 Type of Valve .................................................................................... 207

6.3.2 Multi-Turn Valve ................................................................................ 208

6.3.3 Quarter-Turn Valve ............................................................................ 221

6.4 Introduction to Safety Valve and Relief Valve ............................................ 239

6.5 Relief Concepts ....................................................................................... 241

6.6 Location of Reliefs ................................................................................... 241

6.7 Relief Types ............................................................................................ 243

6.7.1 Spring-Operated Valves ...................................................................... 244

6.7.2 Balanced-Bellows ............................................................................... 244

6.7.3 Rupture Discs ................................................................................... 245

6.8 P&ID for Reactor (Major Equipment) ........................................................ 248

6.8.1 P&ID for Reactor (Major Equipment) ................................................... 248



6.8.2 Justification of The Control System Applied to the Reactor (Major) ....... 249

6.8.3 Justification of the Selection of the Type of Valve and Safety Valve to the

Reactor (Major Equipment) ................................................................ 250

6.9 P&ID For Cumene Column (Minor Equipment) ........................................... 253

6.9.1 P&ID For Cumene Column (Minor Equipment) ..................................... 253

6.9.2 Justification Of The Control System Applied To The Cumene Column .... 254

6.9.3 Justification Of The Selection Of The Type Of Valve And Safety Valve To

The Cumene Column (Minor) ............................................................ 255

7.0 HAZOP ANALYSIS ............................................................................... 258

7.1 HAZOP Analysis For Major Equipment - Reactor ........................................ 258

7.1.1 Recommendation HAZOP For Reactor ................................................. 271

7.2 HAZOP Analysis For Minor Equipment - Cumene Column ........................... 272

7.2.1 Recommendation HAZOP For Cumene Column .................................... 285

8.0 EXPLOSION ANALYSIS ....................................................................... 286

8.1 Introduction to Fire and explosions ........................................................... 286

8.2 Distinction Between Fires And Explosions .................................................. 287

8.3 Mechanism Of Fire And Explosion ............................................................. 288

8.4 Fire Triangle ........................................................................................... 289

8.5 Sources And Causes Of Fire And Explosion In Cumene Plant ...................... 291

8.5.1 Sources Of Fuel ................................................................................. 291

8.5.2 Sources Of Ignition ............................................................................ 292

8.5.3 Sources of Oxygen ......................................................................... 294

8.6 How To Identify Potential Fire And Explosion Sources ................................ 295

8.6.1 Fuel-Hydrocarbon Sources: Identifying And Documenting Hazards ....... 298

8.6.2 Oxygen Sources: Identifying And Documenting Hazards ...................... 300

8.6.3 Energy-Ignition Sources: Identifying And Documenting Hazards ........... 301

8.7 Reasons Why It Is Not Possible To Eliminate All Sources In Fire Triangle .... 304

8.8 Factors Affecting Ignitability Of Flammable Mixtures .................................. 307

8.9 Type Of Explosion Normally Happened In Cumene Plant ............................ 309

8.10 Fire And Explosion Analysis For Major Equipments ................................... 310

8.10.1 Fire And Explosion Analysis For Reactor ............................................ 312



8.10.2 Fire And Explosion Analysis For Cumene Column ............................... 313

8.11 Identify Flammable Inventories And Locations In Cumene Plant ............. 314

8.11.1 Flammable Inventory: Propylene ...................................................... 314

8.11.2 Flammable Inventory: Benzene ........................................................ 316

8.11.3 Flammable Inventory: Di-Isoproply Benzene ..................................... 317

8.11.4 Flammable Inventory: Cumene ......................................................... 318

8.11.5 Flammable Inventory: Propane ......................................................... 319

8.12 Consequence Of Fire And Explosion Events ............................................. 320

8.13 Fire And Explosion Prevention And Control .............................................. 321

8.13.2 Minimization of Potential Amount Of Fuel .......................................... 322

8.13.2 Minimization Of Potential Sources Of Ignition .................................... 323

8.14 Additional Control Measures ................................................................... 325

8.15 Dust Control .......................................................................................... 326

8.16 Ignition Control ..................................................................................... 327

8.17 Damage Control .................................................................................... 328

8.18 Training Of Employees ........................................................................... 329

8.19 Management team ................................................................................ 329

9.0 ENVIRONMENT ANALYSIS .................................................................. 330

9.1 Introduction ............................................................................................ 330

9.2 Analytical Methods .................................................................................. 332

9.3 Emission Sources Of Cumene ................................................................... 333

9.3.1 Anthropogenic Sources ...................................................................... 335

9.4 Environmental Transport, Distribution, And Transformation ....................... 336

9.4.1 Cumene In Atmosphere ..................................................................... 336

9.4.2 Cumene In Water .............................................................................. 337

9.4.3 Cumene In Soil ................................................................................. 339

9.5 Environmental Levels And Human Exposure .............................................. 341

9.5.1 Environmental Levels ......................................................................... 341

9.5.2 Human Exposure ............................................................................... 344

9.6 Comparative Kinetics And Metabolism In Laboratory Animals And Humans . 346

9.7 Effects On Humans, Animals And Vegetation ............................................. 349

9.7.1 Overview of Chemical Disposition ....................................................... 350



9.7.2 Genotoxicity ...................................................................................... 352

9.7.3 Acute and Sub-Acute Effects .............................................................. 353

9.7.4 Sub-Chronic and Chronic Effects ......................................................... 358

9.7.5 Summary of Adverse Health Effects of Cumene Inhalation ................... 365

9.7.6 Effects on Vegetation......................................................................... 368

10.0 COMMERCIAL VALUE ........................................................................ 370

10.1 Cumene Market Survey .......................................................................... 370

10.1.1 Cumene Market Overview ................................................................ 370

10.1.1 Market Survey In Year 2010 (Price Report) ....................................... 371



10.2 Cost Estimation & Economics ................................................................. 375

10.2.1 Background & Objectives ................................................................. 375

10.2.2 Cost Evaluation ............................................................................... 375

10.2.3 Investment ..................................................................................... 377

10.2.4 Project Economic Evaluation ............................................................. 385

10.3 Cumene Commercial Value Report .......................................................... 389

10.3.1 US October cumene prices remain stable amid quiet trade ................. 389

10.3.2 US benzene and RGP markets are quiet ............................................ 390

10.4 Cumene Value Chain ............................................................................. 391

10.5 World Demand Of Cumene .................................................................... 393

10.6 Current Market Situation ........................................................................ 395

10.7 Cumene Market Outlook ........................................................................ 397

10.8 Petrochemicals: Global Markets .............................................................. 398

10.9 Feedstock Requirements ........................................................................ 399

10.10 Case Study .......................................................................................... 402

10.11 Commercial Experience ........................................................................ 404

11.0 CONCLUSION AND RECOMMENDATIONS ......................................... 405

REFERENCES


KC41803 PETROLEUM PROCESSING: GROUP ASSIGNMENT 1 | P a g e

1.0 HISTORY ON PETROLEUM REFINING

Prior to the 19th century, petroleum was known and utilized in various fashions

in Babylon, Egypt, China, Persia, Rome and Azerbaijan. However, the modern history

of the petroleum industry is said to have begun in 1846 when Abraham Gessner

of Nova Scotia, Canada discovered how to produce kerosene from coal. Shortly

thereafter, in 1854, Ignacy Lukasiewicz began producing kerosene from hand-dug oil

wells near the town of Krosno, now in Poland. The first large petroleum refinery was

built in Ploesti, Romania in 1856 using the abundant oil available in Romania.

In North America, the first oil well was drilled in 1858 by James Miller Williams

in Ontario, Canada. In the United States, the petroleum industry began in 1859

when Edwin Drake found oil near Titusville, Pennsylvania. The industry grew slowly

in the 1800s, primarily producing kerosene for oil lamps. In the early 1900's, the

introduction of the internal combustion engine and its use in automobiles created a

market for gasoline that was the impetus for fairly rapid growth of the petroleum

industry. The early finds of petroleum like those in Ontario and Pennsylvania were

soon outstripped by large oil "booms" in Oklahoma, Texas and California.

Prior to World War II in the early 1940s, most petroleum refineries in

theUnited States consisted simply of crude oil distillation units (often referred to as

atmospheric crude oil distillation units). Some refineries also had vacuum distillation

units as well as thermal cracking units such as visbreakers (viscosity breakers, units

to lower the viscosity of the oil). All of the many other refining processes discussed

below were developed during the war or within a few years after the war. They



became commercially available within 5 to 10 years after the war ended and the

worldwide petroleum industry experienced very rapid growth. The driving force for

that growth in technology and in the number and size of refineries worldwide was

the growing demand for automotive gasoline and aircraft fuel.

In the United States, for various complex economic reasons, the construction

of new refineries came to a virtual stop in about the 1980's. However, many of the

existing refineries in the United States have revamped many of their units and/or

constructed add-on units in order to: increase their crude oil processing capacity,

increase the octane rating of their product gasoline, lower the sulfur content of their

diesel fuel and home heating fuels to comply with environmental regulations and

comply with environmental air pollution and water pollution requirements.



1.1 The Malaysian Oil And Gas Industry: An Overview

The Oil & Gas (O&G) industry has seen no small amount of attention during recent

months. One item attracting attention is crude prices rising above USD50 per barrel

(0.159m3) and the simultaneous rise of petrol prices due to reduction in government

subsidies.

News of discoveries of new potentially producing fields has increased interest

in O&G related stocks, whether in suppliers to the industry or oil refineries. To

encourage and maintain this level of interest, IEM held a symposium in July 2004,

attempting to put forward a forum where people outside the O&G industry could be

exposed to issues within the industry.

Petroleum exploration in Malaysia started at the beginning of the 20th century

in Sarawak, where oil was first discovered in 1909 and first produced in 1910. Prior

to 1975, petroleum concessions were granted by state governments, where oil

companies have exclusive rights to explore and produce resources.

The companies then paid royalties and taxes to the government. This state of

affairs ceased on April 1, 1975 as a result of the Petroleum Development Act,

whereby PETRONAS became the custodian of petroleum resources with rights to

explore and produce resources. The national oil company retains ownership and

management control in exploration, development and production of oil resources.

Expenditure and profits are managed under instruments called Production Sharing

Contracts (PSCs). The Production Sharing Contractor assumes all risks and sources



all funds for all petroleum operations. The Contractor receives an entitlement

through production.

Figure 1.1 Production Sharing Contractor Entitlement

Each PSC may have different terms and conditions. For example, different

time periods are allowed for exploration of acreage, developing and installing

infrastructure to produce any hydrocarbons discovered, and the actual production

period.

Malaysia has the 25th largest oil reserves and the 14th largest gas reserves in

the world. The total reserves is of the order of 18.82 billion barrels oil equivalent

(boe), with a crude production rate of 600 thousand barrels per day.



Figure 1.2 Historical Crude Oil Production (bbls : barrels per day. SB :

Sabah contribution. SK : Sarawak Contribution, PM : Peninsular

contribution.)

The average natural gas production stands at approximately 5.7 billion

standard cubic feet per day. Malaysia has 494,183km2 of acreage available for oil

and gas exploration, with 337,167 km2 in the offshore continental shelf area, and

63,968km2 in deepwater.

The acreage is split into 54 blocks, out of which 28 (a total of 205,500km2)

are currently operated by Petronas Carigali Sdn. Bhd. plus seven other multinational

oil companies.



Figure 1.3 Historical Natural Gas Production



Figure 1.4 Increased production through rejuvenation

There is also an opportunity to increase production by rejuvenation of existing

production facilities. This concept can be applied both to topside and subsurface

facilities. As an example, more than 50% of Malaysian assets have been producing

for longer than 15 years. There are definite opportunities to debottleneck facilities,

looking at design and current operating conditions, and maximising the use of

existing equipment. New technologies may be retrofitted into existing equipment,

increasing capacity at an acceptable cost.



Figure 1.5 Competitiveness of the Industry

Although there are few lower cost centres in this region, the international

clients still prefer Malaysia due to its high quality engineering produced and

availability of up to date technology knowledge. The Oil and Gas industry can be

split into upstream and downstream sectors. The upstream sector includes the

exploration and the extraction of crude oil.

In the Malaysian Oil and Gas sector, it has been the upstream sector that has

traditionally been developed. The Petroleum Development Act 1974 governs the

upstream and the downstream sectors of the petroleum industry under which

Petronas is party of. Petronas has a licensing system. All work which is contracted

out in the upstream sector is through licensed contractors. One of the objectives of



the Act was to make sure local players were involved. One of the requirements to

obtain a licence is being a local company. It is because of this that the oil and gas

engineering industry was fully developed by the mid 80s. From the mid 80s to late

80s, all engineering design work had to be done locally.

According to Ir. Dr Torkil Ganendra, Secretary of MOGEC and Director of Aker

Kvaerner Asia Pacific, the Oil and Gas industry in Malaysia is a regulated industry,

thus all upstream engineering works have to be performed locally if there was local

technical capability. Some specialised areas are done overseas.



1.2 Flow Diagram of Typical Refinery

The image below is a schematic flow diagram of a typical oil refinery that depicts the

various unit processes and the flow of intermediate product streams that occurs

between the inlet crude oil feedstock and the final end products.

The diagram depicts only one of the literally hundreds of different oil refinery

configurations. The diagram also does not include any of the usual refinery facilities

providing utilities such as steam, cooling water, and electric power as well as storage

tanks for crude oil feedstock and for intermediate products and end products.

There are many process configurations other than that depicted above. For

example, the vacuum distillation unit may also produce fractions that can be refined

into end products such as: spindle oil used in the textile industry, light machinery oil,

motor oil, and various waxes.



Figure 1.6 Schematic Flow Diagram of typical oil refinery

(Source: http://en.wikipedia.org/wiki/Oil_refinery)



1.3 Introduction On Cumene

The cumene molecule can be visualized as a straight-chain propylene group

having a benzene ring attached at the middle carbon , C6H5CH(CH3)2 . It is a

colourless liquid , bp 152.40C having a characteristic aromatic odor . It is isomeric

with n-propylbenzene , ethyltoluene and trimethylbenzene.

Figure 1.7 Chemical Structure Of Cumene

(Source: http://en.wikipedia.org/wiki/Cumene)

Cumene is the common name for isopropylbenzene, an organic

compound that is an aromatichydrocarbon. It is a constituent of crude oil and

refined fuels. It is a flammable colorless liquid that has a boiling point of 152 C.

Nearly all the cumene that is produced as a pure compound on an industrial scale is



converted to cumene hydroperoxide, which is an intermediate in the synthesis of

other industrially important chemicals, primarily phenol andacetone.

Thus cumene is also named as 1-methylethyl benzene or 2-phenyl-propane or

isopropylbenzene. Cumene (C9H12) is a substituted aromatic compound in the

benzene , toluene and ethylbenzene series.

Cumene is a clear liquid at ambient conditions. High purity cumene is

normally manufactured from propylene and benzene and is a minor constituent of

most gasolines. It is the principal chemical used in the world wide production of

phenol and its co-product acetone.

Many consumer or industrial products such as plywood and composition board

banded with phenolic resins, nylon-6, epoxy and polycarbonate resins and solvents,

have origins that can be traud to cumene.

Cumene processes were originally developed between 1939 and 1945 to meet

the demand for high octane aviation gasoline during world war-II. In 1989 about

95% of cumene demand was as an intermediate for the production of phenol and

acetone. A small percentage is used for the production of -Methylstyrene.

Before the devolopement of the cumene route to phenol and acetone,

cumene had been used extensively during warld war2. It is a curious fact that

although propylation of benzene by means of phosphoric acid and aluminium

chloride have been the standard methods of manufacture for many years ,the first



plan used sulphuric acid as a catalyst. This was a war time expedient arising from

uncertainity over phosphoric acid supplies.

Almost all the worlds supply of cumene is now produced as an intermediate for

phenol and acetone manufacture. Some refinery units still produce cumene for use

as an antiknock constituent of gasoline but it is doubtful whether new plants would

be constructed for this purpose .

Neither does it seem likely that any large scale plant would be installed for

manufacturing the hydroperoxide, methylstyrene ,diisopropylebenzene,or

acetophenone ,although these cumene derived compounds are of considerable

commercial importance. They occur as byproducts during cumene and phenol

production, and are usually marketed by manufacturers .



1.4 Cumene Production

Commercial production of cumene is by FriedelCrafts alkylation of

benzene with propylene. Previously, solid phosphoric acid (SPA) supported

on alumina was used as the catalyst. Since the mid-1990s, commercial production

has switched to zeolite-based catalysts.

Isopropyl benzene is stable, but may form peroxides in storage if in contact

with the air. It is important to test for the presence of peroxides before heating or

distilling. The chemical is also flammable and incompatible with strong oxidizing

agents. Environmental laboratories commonly test isopropyl benzene using a Gas

chromatographymass spectrometry (GCMS) instrument.



1.5 Cumene Properties

Cumene

IUPAC name

(1-methylethyl)benzene

Other names

isopropylbenzene

2-phenylpropane

Identifiers

CAS number 98-82-8

PubChem 7406

ChemSpider 7128

UNII 8Q54S3XE7K



KEGG C14396

ChEBI CHEBI:34656

RTECS number GR8575000

Jmol-3D images Image 1

Properties

Molecular formula C9H12

Molar mass 120.19 g mol1

Appearance colorless liquid

Density 0.862 g cm3, liquid

Melting point 96 C, 177 K, -141 F

Boiling point 152 C, 425 K, 306 F

Solubility in water Insoluble

Viscosity 0.777 cP at 21 C

Hazards

R-phrases R10,R37,R51/53,R65



S-phrases S24,S37,S61,S62

Main hazards Flammable

Flash point 43 C

Related compounds

Related compounds ethylbenzene, toluene, benzene



1.6 Cumene Process

The Cumene process (Cumene-phenol process, Hock process) is

an industrial process for developing phenol & acetone from benzene and propylene.

The term stems from cumene (isopropyl benzene), the intermediate material during

the process. It was invented by Heinrich Hock in 1944 and independently by R. dris

and P. Sergeyev in 1942 (USSR).

This process converts two relatively cheap starting

materials, benzene and propylene, into two more valuable ones, phenol and acetone.

Other reactants required are oxygen from air and small amounts of a radical initiator.

Most of the worldwide production of phenol and acetone is now based on this

method. In 2003, nearly 7 billion kg of phenol was produced by the Hock Process.



1.7 Technical Description

Benzene and propylene are compressed together to a pressure of 30 standard

atmospheres at 250 C (482 F) in presence of a catalytic Lewis acid. Phosphoric

acid is often favored over aluminium halides. Cumene is formed in the gas-

phase Friedel-Crafts alkylation of benzene by propylene:

Cumene is oxidized in air which removes the tertiary benzylic hydrogen from

cumene and hence forms a cumene radical:



1.8 Cumene Chemical Properties

Cumene is a colourless liquid, soluble in alcohol, carbon tetra chloride, ether and

benzene. It is insoluble in water. Cumene is oxidized in air which removes the

tertiary benzylic hydrogen from cumene and hence forms a cumene radical:

This cumene radical then bonds with an oxygen molecule to give

cumene hydroperoxide radical, which in turn forms cumene

hydroperoxide (C6H5C(CH3)2-O-O-H) by abstracting benzylic hydrogen from another

cumene molecule.

This latter cumene converts into cumene radical and feeds back into

subsequent chain formations of cumene hydroperoxides. A pressure of 5 atm is used

to ensure that the unstable peroxide is kept in liquid state.



Cumene hydroperoxide is then hydrolysed in an acidic medium (the Hock

rearrangement) to givephenol and acetone. In the first step, the terminal

hydroperoxy oxygen atom is protonated.

This is followed by a step in which the phenyl group migrates from the benzyl

carbon to the adjacent oxygen and a water molecule is lost, producing

a resonance stabilized tertiary carbocation.

The concerted mechanism of this step is similar to the mechanisms of

the Baeyer-Villiger oxidationand also the oxidation step of hydroboration-

oxidation.[6] In 2009, an acidified bentonite clay was proven to be a more

economical catalyst than sulfuric acid as the acid medium.



As shown below, the resulting carbocation is then attacked by water, a proton

is then transferred from the hydroxy oxygen to the ether oxygen, and finally the ion

falls apart into phenol and acetone.

The products are extracted by distillation.



1.9 Uses Of Cumene

1. As feed back for the production of Phenol and its co-product acetone

2. The cumene oxidation process for phenol synthesis has been growing in

popularity since the 1960s and is prominent today. The first step of this

process is the formation of cumene hydroperoxide. The hydroperoxide is

then selectively cleaved to Phenol and acetone.

3. Phenol in its various formaldehyde resins to bond construction materials like

plywood and composition board (40% of the phenol produced) for the

bisphenol A employed in making epoxy resins and polycarbonate (30%) and

for caprolactum, the starting material for nylon-6 (20%). Minor amounts are

used for alkylphenols and pharmacuticals.

4. The largest use for acetone is in solvents although increasing amounts are

used to make bisphenol A and methylacrylate.

5. - Methylstyrene is produced in controlled quantities from the cleavage of

cumene hydroperoxide, or it can be made directly by the dehydrogenation

of cumene.

6. Cumene in minor amounts is used as a thinner for paints, enamels and

lacquers and to produce acetophenone, the chemical intermediate

dicumylperoxide and diiso propyl benzene.

7. Cumene is also used as a solvent for fats and raisins.



1.10 Description On Q-Max Process

The most promising materials were modified to improve their selectivity and then

subjected to more-rigorous testing. By 1992, UOP had selected the most promising

catalyst based on beta-zeolite for cumene production and then began to optimize

the process design around this new catalyst. The result of this work is the Q-Max

process and the QZ- 2000 catalyst system.

1. Raw material propylene and benzene are used for the production of cumene.

2. These are stored in the respective storage tanks of 500MT capacity in the

storage yard pumped to the unit by the centrifugal pumps.

3. Benzene pumped to the feed vessel which mixes with the recycled benzene.

Benzenestream is pumped through the vaporizer with 25 atm pressure and

vaporized to the temperature of 243degC, mixed with the propylene which is

of same and temperature and pressure of benzene stream.

4. This reactant mixture passed through a fired super heater where reaction

temperature 350degC is obtained.

5. The vapor mixture is sent to the reactor tube side which is packed with the

solid phosphoric acid catalyst supported on the kieselguhr the exothermal

heat is removed by the pressurized water which is used for steam production

and the effluent from the reactor i.e., cumene, p-DIPB, unreacted benzene,

propylene and propane with temperature 350oC is used as the heating media

in the vaporizer which used for the benzene vaporizing and cooled to 40oC in

a water cooler, propylene and propane are separated from the liquid mixture

of cumene, p-DIPB, benzene in a separator operating slightly above atm and



the pressure is controlled by the vapor control value of the separator, the fuel

gas is used as fuel for the furnace also.

6. The liquid mixture is sent to the benzene distillation column which operates at

1 atm pressure, 98.1% of benzene is obtained as the distillate and used as

recycle and the bottom liquid mixture is pumped at bubble point to the

cumene distillation column where distillate 99.9% cumene and bottom pure

p-DIPB is obtained.

7. The heat of bottom product p-DIPB is used for preheating the benzene

column feed, All the utility as cooling water, electricity, steam from the boiler,

pneumatic air are supplied from the utility section

8. The typical reactor effluent yield contains 94.8 Wt. % cumene and 3.1 Wt. %

of diiso propylbenzene. The remaining 2.1 % is primarily heavy aromatics.

9. This high yield of cumene is achieved without transalkylation of diiso

propylbenzene and is unique to the solid phosphoric acid catalyst process.

10. The cumene product is 99.9 Wt. % pure and the heavy aromatics, which have

an octane number of 109, can either be used as high octane gasoline

blending components or combined with additional benzene and sent to a

transalkylation section of the plant where diiso propylbenzene is converted to

cumene.

11. The overall yields of cumene for this process are typically 97-98 Wt. % with

transalkylation and 94-96 Wt. % without transalkylation.



2.0 REFINERY BALANCE

2.1 Introduction

Changes such as structural and cyclical in our business environment have keep us on

our toes. Our core businesses are changing in our historic home of Europe. The

Consumption of both chemicals and petroleum products is down and new demands

for more diesel and less gasoline, greener products and so on which are taking shape

currently.

We are not surprise to any changes that come to us. Since we had foreseen

most of them and are now adjusting our production base accordingly, while deploying

all our innovation capabilities to create a line of products in sync with our customers

expectations.

In addition, we are setting the stage for our expansion in regions of strong

economic growth at the same time such as Asia, the Middle East and Africa, and

adapting to the specific needs of those markets, by leveraging solid partnerships and

the remarkable agility of all our activities.

Total (37.5%) and Saudi Aramco (62.5%) are partners in SATORP, the

company building the Jubail refinery in Saudi Arabia. This strategically important

project will allow us to move closer to oil and gas fields and consumers.



2.2 The Abu Dhabi Oil Refining Company (Takreer)

Basically, The Abu Dhabi Oil Refining Company (Takreer) was established in 1999 in

order to take over the responsibility of refining operations previously undertaken by

the Abu Dhabi National Oil Company (ADNOC). There are several companys areas of

operation which include the refining of crude oil and condensate, supply of petroleum

products and production of granulated Sulphur in compliance with domestic and

international specifications. Moreover, this refinery can work for 85,000 bbl/day

capacity.

Figure 2.1: The PMC contract is for the EPC phase of the base oils plant in

Ruwais Industrial Complex.



Today, The Shaw Group Inc. had announced that their company has been

awarded a contract by The Abu Dhabi Oil Refining Company (Takreer) to provide

project management consultancy services during the engineering, procurement and

construction phase of a base oils plant at the Ruwais Industrial Complex in Abu Dhabi.

Basically, the planned facility will be capable of producing 500,000 tons/year of

Group III base oils, as well as 100,000 tons/year of Group II base oils, and is scheduled

to begin commercial production in 2013. Group II and III base oils are used for

blending top-tier lubricants for car engines.

Besides, an announcement was made by UOP LLC, a Honeywell company, that

they have been selected by the Abu Dhabi Oil Refining Company, also known as

Takreer, with the aim to supply technology and engineering services for an expansion

at its Ruwais Refinery in the United Arab Emirates.



The history of the refineries in Abu Dhabi Refinery which consists of

85000bbl/day is shown in Figure 2.2 below:

Figure 2.2: history of the refineries in Abu Dhabi Refinery which consists

of 85000bbl/day

1996Plant Expansion 85,000 BBL/day

1983New Refinery 60,000 BBL/day

1976Original Plant 15,000 BBL/day



The history of the refineries in Ruwais Refinery which consists of 40000bbl/day

is shown in below:

Figure 2.3: History of the refineries in Ruwais Refinery which consists of

40000bbl/day

There are other facilities such as below:

Power Geeration 660MW

Water Desalination 14.0 MM Gallons/ day

Hazardous Material Treatment, 26MMT/Year

2006

Gasoline Units

2000

Condensate units 280,000 BBL/day

1985

Hydrocracker units

1981

Hydro-skimmer units 120,000BBL/day



2.3 Refinery Installations

After the discovery of oil in Abu Dhabi in year 1958 and the first export shipments of

Crude in year 1962, there are a plans to build a glass root Refinery with a capacity of

15,000 barrels per stream day (BPSD) to meet a growing local need for petroleum

products. Basically, the construction work has begun in year 1973. This work cost

around initial $45 million and this plant was inaugurated in the April of 1976.

Therefore, we can see that the demand for oil products were grow rapidly.

However, the work began almost on installing a new Refinery to process a further

60,000 BPSD and this was commissioned in year 1983.

So, requirements has continued to grow in the fast-developing Emirate and

ADNOC has decided to expand the capacity yet again with environmental

considerations in mind and to include additional units for Gas Oil Desulphurization and

Sulphur recovery. Therefore, the expanded Refinery with a capacity rate of 85,000

BPSD has been started up in December 1992.

On the other hand, a Salt and Chlorine Plant has been commissioned at Umm

Al Nar in the year of 1981 which was merged with the Refinery in year 1990 in order

to form the Abu Dhabi Refinery and Chlorine Division.

On 30th November 2001, it was permanently shut down. Two power plants,

owned and operated by Umm Al Nar Power Company, and a Lube oil blending/filling

plant, owned and operated by ADNOC Distribution, are located adjacent to the

Refinery.



The refinery is a Hydro Skimming Complex designed to process Bab Crude as

well as a mixture of Asab-Sahil, Shah and Thammama Condensate. Finished products

from the Refinery are as follows: Liquefied Petroleum Gases, Naphtha, Unleaded

Gasoline, Aviation Turbine Kerosene, Domestic Kerosene, Gas Oil, Straight Run

Residue, Liquid Sulphur.

2.3.1 Refinery Units

Therefore, the refinery unit including:

1. Crude Distillation Unit (85,000 BPSD)

2. Naphtha Hydrodesulphuriser Unit (22,795 BPSD)

3. Kerosene Merox Unit (21,250 BPSD)

4. Catalytic Reformer Unit (14,000 BPSD)

5. Gas Oil Hydrodesulphuriser Unit (22,500 BPSD)

6. LPG Treating and Recovery Unit (3,480 BPSD)

7. Excess Naphtha Stabilizer Unit (3,325 BPSD)

8. Gas Sweetening Unit (35 tons/day H2S Removal)

9. Sulphur Recovery Unit (35 tons/day)

10. Jarn Yaphour Crude Oil Stabilization Plant (10,000 BPSD)



2.3.1.1 Crude Distillation Unit (85,000 BPSD)

For initial step, prior to the actual distillation process, Crude Oil is passed

through a Desalter Unit to remove the undesirable salts, water and sludge

which are generally associated with any type of crude.

After final heating in a furnace, the Crude is then fractionated in the

Atmospheric Distillation Column into the basic raw petroleum fractions of

Naphtha, kerosene, Gas Oil and Straight Run Residue.

2.3.1.2 Naphtha Hydrodesulphuriser Unit (22,795 BPSD)

The Naphtha Hydrodesulphuriser sweetens the Straight Run Naphtha from

Crude Unit.

This unit has produced three products namely: Heavy Naphtha, Light Naphtha

and Sour Liquefied Petroleum Gases.

2.3.1.3 Kerosene Merox Unit (21,250 BPSD)

Mercaptans was converted by the unit in the straight run kerosene into

disulphine in order to meet the final product quality for aviation kerosene.

2.3.1.4 Catalytic Reformer Unit (14,000 BPSD)

The Reformer processes the Heavy Naphtha cut to improve its anti-knock

properties prior to using it as a Gasoline blending component.



2.3.1.5 Gas Oil Hydrodesulphuriser Unit (22,500 BPSD):

Gas oil sulphur content has been reduced by the Gas Oil Hydrodesulphurise to

0.15 wt% in order to improve the product quality.

2.3.1.6 LPG Treating and Recovery Unit (3,480 BPSD):

In this unit, raw LPG from Naphtha Hydrodesulphuriser and Catalytic Reformer

Unit are processed.

The butane that produced in this unit is used as a blending component in

Gasoline.

Besides that, the butane also can blended with Propane in order to form LPG

for domestic use.

2.3.1.7 Excess Naphtha Stabilizer Unit (3,325 BPSD):

Excess Naphtha from Crude Unit is stabilized.

2.3.1.8 Gas Sweetening Unit (35 tons/day H2S Removal):

Amine solution was used to sweetens the sour gas that produced in the refinery

facilities so that to remove any hydrogen sulphide inn order to minimize sulphur

oxide emissions.



2.3.1.9 Sulphur Recovery Unit (35 tons/day):

The acid gases produced from Gas Sweetening Unit are converted to liquid

sulphur.

2.3.1.10 Jarn Yaphour Crude Oil Stabilization Plant (10,000 BPSD):

The Oil/Gas Separation Plant is designed to stabilize Crude from Jarn Yaphour

Wells, located some 30 kilometers from Abu Dhabi.

The separated gas is further treated to remove hydrogen sulphide, water and

hydrocarbon condensate before it is injected into GASCOs Main Gas Network.

2.3.2 Utilities, Off-sites, Terminal & ADR Technology

Additional Effluent Water Treatment facilities were installed to adhere to rigid oil in

water specification of 10 ppm maximum.

2.3.2.1 Utilities

Power and fresh was supplied from the adjacent plant of the Abu Dhabi Water

and Electricity Authority to the refinery.

Steam, Air, Nitrogen and Sea Water for cooling are all provided by the Refinery's

own facilities.

The Refinerys Fuel Gas supply is supplemented by Natural Gas from the GASCO

Main Network.



2.3.2.2 Off-sites

The storage capacity of Abu Dhabi Refinery Tank Farm is 500,000 cubic meters,

which includes facilities for Crude Oil, Intermediate Streams, Semi-Finished

Products, Finished Products and Utility Fuel Oil.

The Residue and Naphtha are shipped to Ruwais Refinery while most of the

Refined Products from Abu Dhabi Refinery are sold in the ever expanding

domestic market.

2.3.2.3 Marine Terminal

The Refinery is served by a two-Berth Marine Terminal on the North Shore of

the Island for loading and unloading of tankers.

Maximum Draft is 9.5 meters; maximum Cargo is 30,000 tons.

2.3.2.4 ADR Technology

Abu Dhabi Refinery completed the process of installing a fully integrated state-

of-the-art Computerized System designed to Modernize Operations in the year

1994.

In January 1993, the first level was achieved with the commissioning of a new

Consolidated Control Room under the overall Refinery expansion project.

The Refinery is equipped with a Distributed Control System (DCS).



DCS allowed for the introduction of an Advanced Process Control system as

part of the Process Automation and Computerization project (PACS).

PACS are designed to provide accurate and up-to-the-minute information on

every aspect of the Operations in Support of Operational and Management

Activities.

On the other hand, the second level of the project includes the implementation

of Advanced Process Control (APC) strategies and off-site Automation and

Computerization.

Third level involved the implementation of a plant-wide Data Base and

Communications Network, leading to the use of a Computerized Decision

Support System in laboratory management, Planning, Scheduling, Mass

Balancing, Oil Accounting and Performance Monitoring.



CRUDE DISTILLATION UNIT

NAPHTHA HYDRODESULPHURISER UNIT

KEROSENE MEROX UNIT

CATALYTIC REFORMER UNIT

GAS OIL HYDRODESULPHURISER UNIT

LPG TREATING AND RECOVERY UNIT

EXCESS NAPHTHA STABILIZER UNIT

GAS SWEETENING UNIT

SULPHUR RECOVERY UNIT

CRUDE OIL STABILIZATION PLANT

85 000 BPSDFrom crude oil to fraction of naphtha, kerosene, gas oil and straight run residue

22 795 BPSDFrom straight run naphtha to heavy naphtha, light naphtha and sour liquefied petroleum gaese

21 250 BPSDFrom mercaptans to disulphide

14 000 BPSDFrom heavy naphtha cut to gasoline blending component

22 500 BPSDProduct: Reduced sulphur content of gas oil

3 480 BPSDProduct: Processed LPG

3 325 BPSDProduct: Stabilized naphtha

35 tons/day H2S removalProduct: Sweetened sour gases

35 tons/dayFrom acid gases to liquid sulphur

10 000 BPSDProduct: Stabilized crude

ABU DHABI REFINERY

Figure 2.4: Overall operation in Abu Dhabi Oil Refinery Company



2.4 Mass Balance Based 400,000 BPD of Middle East Heavy Crude

By referring to US Petroleum Refinery Balance (Millions Barrels Per Day, Except Utilization Factor) as shown below:

Figure 2.5: US Petroleum Refinery Balance (Millions Barrels Per Day, Except Utilization Factor)



2.4.1 Mass Balance by Assumed Proportion of Refining Products is Double

Figure 2.6: By referring to the diagram above which consists of 200,000

barrels per day

(Source: Environmental Aspects in Refineries and Projects, 2012)



It is found that if the feedstock which is the 400 000 BPD Middle East heavy crude and assumed that the proportion of the refining

products is double and the number of the condensate is 560,000bbl/day, the final product will be shown in Table 2.1 below:

Table 2.1: Calculation of final product from 400 000 BPD Middle East heavy crude

Products

Quantity

(200,000 BPD) Fraction Percentage (%)

Mass balance

(400,000 BPD)

Gasoline 55000 0.138 13.836478 110000

Fuel oil 31000 0.078 7.798742138 62000

Jet fuel & kerosene 112000 0.2818 28.17610063 224000

Gas oil 89000 0.2239 22.38993711 178000

LPG 16000 0.0403 4.025157233 32000

Naphta 94500 0.2377 23.77358491 189000

Total 397500 1 100 795000



Figure 2.7: Comparison quantity of product produced

110000

62000

224000

178000

32000

189000

795000

0

100000

200000

300000

400000

500000

600000

700000

800000

900000

Gasoline Fuel oil Jet fuel &kerosene

Gas oil LPG Naphta Total

Mass balance (400000bbl/d) (BPD)



2.4.2 Mass Balance by Fraction Method

Based on the production of Abu Dhabi Oil Refining Company (refinery plant) at the

year of 1996, the mass balance is done using fraction method.

Table 2.2: Calculation of final product from 400 000 BPD Middle East

heavy crude

Products Quantity

(BPD) Fraction

Percentage

(%)

Mass balance

(BPD)

Gasoline 46100 0.199222 19.92 79688.85048

Fuel oil 67000 0.289542 28.95 115816.7675

Jet fuel & kerosene 36200 0.156439 15.64 62575.62662

Gas oil 70000 0.302506 30.25 121002.5929

LPG 7100 0.030683 3.07 12273.12014

Asphalt 5000 0.021608 2.26 8643.042351

Total 231400 1 100 400 000

** This analysis is done based on a production rate from Abu Dhabi Oil Refining

Company (refinery plant) using heavy crude oil




0

20000

40000

60000

80000

100000

120000

140000

QU

AN

TITY

(B

PD

)

PRODUCT

Gasoline Fuel oil Jet fuel & kerosene Gas oil LPG Asphalt



2.4.3 Mass Balance based on Total Production from while Middle East Countries

There can be another analysis based on the total production from whole Middle East countries

MIDDLE EAST COUNTRIES STATISTIC

Table 2.3: Middle East Output of Refined Petroleum Products, 2005 (Thousand Barrels per Day)

Energy Information Administration, International Energy Annual 2006 Table Posted: December 8, 2008

Country

Motor

Gasoline

Jet

Fuel

Kerosene

Distillate

Fuel

Oil

Residual

Fuel

Oil

Liquefied

Petroleum

Gases

Other

Total Output of

Refined Petroleum

Products

Refinery

Fuel and

Loss

Bahrain 17.64 49.45 8.47 91.97 52.13 1.18 47.63 268.47 10.74

Iran 260.67 18.47 127.66 499.57 480.16 135.58 166.82 1,688.93 67.56

Iraq 74.43 12.82 23.19 104.40 152.15 36.61 51.83 455.44 17.52

Israel 63.78 24.16 3.37 62.22 49.95 18.32 23.12 244.90 9.42

Jordan 14.33 7.04 4.89 28.53 27.91 3.87 5.15 91.73 3.53

Kuwait 65.48 50.27 128.30 245.77 179.47 149.41 222.99 1,041.68 40.06

Lebanon 0 0 0 0 0 0 0 0 0



Oman 14.84 3.69 0.23 14.61 34.92 2.42 0.48 71.20 2.85

Qatar 40.31 20.10 0.08 18.94 14.23 81.83 5.67 181.16 6.97

Saudi Arabia 347.63 143.98 81.51 647.59 487.58 34.90 343.49 2,086.68 83.47

Syria 31.95 4.80 1.14 74.96 88.01 10.77 43.19 254.81 9.80

United Arab Emirates 43.73 117.71 0 87.41 28.67 16.63 93.27 387.42 14.90

Yemen 27.93 8.02 2.31 19.61 8.24 3.09 6.73 75.93 2.92

Middle East 1,002.71 460.50 381.16 1,895.59 1,603.44 494.59 1,010.36 6,848.35 269.73



Figure 2.9: Fraction of Middle East Output on 2005

motor gasoline15%

jet fuel7%

kerosene5%

fuel oil28%

fuel oil23%

petroleum gases7%

other15%

Middle East Output of Refined Petroleum Product on 2005

motor gasoline jet fuel kerosene fuel oil fuel oil petroleum gases other



Table 2.4: Calculation of final product from 400,000 BPD Middle East

heavy crude

Products Quantity

(BPD) Fraction

Percentage

(%)

Mass balance

(BPD)

Gasoline 1002.71 0.146416 14.64 58566.51602

Fuel oil 1895.59 0.276795 27.68 110718.0562

Jet fuel 460.5 0.067242 6.72 26896.98979

Kerosene 381.16 0.055657 5.57 22262.88084

LPG 494.59 0.07222 7.22 28888.12634

Asphalt 1010.36 0.147533 14.75 59013.33898

Residual fuel oil 1603.44 0.234135 23.41 93654.09186

TOTAL 6848.35 1 100 400 000




0

20000

40000

60000

80000

100000

120000

Qu

anti

ty (

BP

D)

Product

Gasoline Fuel oil Jet fuel Kerosene LPG Asphalt Residual fuel oil



2.5 Conclusion

With the increasing world energy demand, this situation has pushed the oil producing

countries, Middle East Countries, to start exploiting heavy oil reservoirs, which had

been neglected or little used and to increase the oil exploration activities. Currently,

there are some heavyweight producers such as Saudi Arabia, Venezuela and Iran

produce large quantities of heavy ( API < 20) sour crude with high sulfur content.

However, others such as Nigeria, the United Arab Emirates, Angola and Libya pump a

higher quality, light sweet crude, with low sulfur content.

Since the global energy demand is keep increasing, this has putting up pressure

on the major oil producing countries to increase their production capacities. With

Middle East Countries alone, the production capacity is expected to reach 4 million

barrels per day (MBPD) by the year of 2020 has reach.

It is important for the Middle East Countries to maintain its market share

besides increase production capacity. However, heavy crude oil (API < 20) must be

also used as gap filler.

Basically, these current events are facing the oil industry in Middle East

Countries with many decisions and technological challenges, including counteracting

expected increased risk of corrosion and equipment failures during the production and

refining of heavy crude oil. Inorganic salts, organic chlorides, organic acids, and sulfur

compounds can be consider as the most damaging impurities.



Things might getting worst when many of the compounds are unstable during

refining operations and they break into smaller components or combine with other

constituents, concentrating corrodants in certain units, such as the breakdown of

sulfur compounds and organic chlorides.

However, most of the world refineries including Kuwait are equipped with alloys

that capable of handling sweet light crude, which is most suitable for refining into

petrol, gas oil and heating oil. On the other hand, refining of heavy crude is difficult

and is associated with operational problems.

Problem can be arise from the increased risk of corrosion, equipment failures,

and downtime of process units. This problem are caused by the high sulfur and salt

contents of these crudes including organic chlorides.



3.0 GROUP PROJECT

3.1 Introduction To Cumene Production

The commercial production of cumene is by FriedelCrafts alkylation of

benzene with propylene. In previously, solid phosphoric acid (SPA) supported

on alumina was used as the catalyst. Therefore, since the mid-1990s, commercial

production has switched to zeolite-based catalysts.

Isopropyl benzene is stable, but may form peroxides in storage if in contact

with the air. It is important to test for the presence of peroxides before heating or

distilling. The chemical is also flammable and incompatible with strong oxidizing agents.

Environmental laboratories commonly test isopropyl benzene using a Gas

chromatographymass spectrometry (GCMS) instrument.

3.1.1 Cumene Project Definition

Isopropylbenzene, also known as cumene, is among the top commodity chemicals,

taking about 7 8% from the total worldwide propylene consumption. Today, the

cumene is used almost exclusively for manufacturing phenol and acetone.

This case study deals with the design and simulation of a medium size plant of

100 kton cumene per year. The goal is performing the design by two essentially

different methods. The first one is a classical approach, which handles the process

synthesis and energy saving with distinct reaction and separation sections. In the

second alternative a more innovative technology is applied based on reactive

distillation.



Table 3.1 presents the purity specifications. The target of design is achieving

over 99.9% purity. It may be seen that higher alkylbenzenes impurities are undesired.

Ethyl - and butylbenzene can be prevented by avoiding olefi ns and butylenes in the

propylene feed. N - propylbenzene appears by equilibrium between isomers and can

be controlled by catalyst selectivity.

In this project we consider as raw materials benzene of high purity and

propylene with only 10% propane. As an exercise, the reader can examine the impact

of higher propane ratios on design.

Table 3.1: Specifications For Cumene



3.1.2 Cumene Manufacturing Routes

General information about chemistry, technology and economics can be found in the

standard encyclopaedic material, as well as in more specialized books. The

manufacturing process is based on the addition of propylene to benzene (Alexandre,

2008):

Beside isopropyl benzene (IPB) a substantial amount of polyalkylates is formed

by consecutive reactions, mostly as C6H5 - (C3H7) 2 (DIPB) with some C6H5 - (C3H7)

3 (TPB). The main reaction has a large exothermal effect, of 113 kJ/mol in standard

conditions. The alkylation reaction is promoted by acid - type catalysts.

The synthesis can be performed in gas or liquid phase. Before 1990 gas phase

alkylation processes dominated, but today liquid - phase processes with zeolite

catalysts prevail. Recent developments make use of reactive distillation.

Cumene processes based on zeolites are environmentally friendly, offering high

productivity and selectivity. The most important are listed in Table 3.2. The catalyst

performance determines the type and operational parameters of the reactor and,

accordingly the flowsheet configuration. The technology should find an efficient

solution for using the reaction heat inside the process and and/or making it available

to export. By converting the polyalkylbenzenes into cumene an overall yield of nearly

100% may be achieved.



Table 3.2: Technologies for cumene manufacturing based on zeolites

Figure 3.1 illustrates a typical conceptual flowsheet. Propylene is dissolved in a

large excess of benzene (more than 5 : 1 molar ratio) at sufficiently high pressure that

ensures only one liquid phase at the reaction temperature, usually between 160 and

240 C. The alkylation reactor is a column filled with fixed-bed catalyst, designed to

ensure complete conversion of propylene. The reactor effluent is sent to the

separation section, in this case a series of four distillation columns: propane (LPG)

recovery, recycled benzene, cumene product and separation of polyisopropylbenzenes.

The flowsheet involves two recycles: nonreacted benzene to alkylation and

polyalkylbenzenes to transalkylation. The minimization of recycle flows and of energy

consumption in distillation are the key objectives of the design.

These can be achieved by employing a highly active and selective catalyst, as

well as by implementing advanced heat integration.



Figure 3.1: Conceptual Flowsheet for cumene manufacturing by Dow-

kellogg process



3.1.3 General Overall Material Balance for Cumene Process

Table 3.3 illustrates a typical material balance of a cumene plant using Dow-Kellog

technology. The propylene may contain up to 40% propane, but without ethylene and

butylene. Beside cumene, variable amounts of LPG can be obtained as subproducts.

Energy is also exported as LP steam, although it is consumed as well as other utilities

(fuel, cooling water, electricity).

Table 3.3: Overall Process Material Balance After Dow-Kellog Technology



3.1.4 Physical Properties

Table 3.4 presents some fundamental physical constants. Critical pressures of propane

and propylene are above 40 bar, but in practice 20 to 30 bar are sufficient to ensure

a high concentration of propylene in the coreactant benzene. From the separation

viewpoint one may note large differences in the boiling points of components and no

azeotrope formation. In consequence, the design of the separation train should not

raise particular problems. Since the liquid mixtures behave almost ideally a deeper

thermodynamic analysis is not necessary. The use of vacuum distillation is expected

because of the high boiling points of the polyalkylated benzenes.

Table 3.4: Basic physical properties of components in the outlet reactor

mixture



3.2 Cumene Process

The Cumene process (Cumene-phenol process, Hock process) is an industrial

process for developing phenol and acetone from benzene and propylene. The term

stems from cumene (isopropyl benzene), the intermediate material during the process.

It was invented by Heinrich Hock in 1944 and independently by R. dris and P.

Sergeyev in 1942 (USSR).

This process converts two relatively cheap starting

materials, benzene and propylene, into two more valuable ones, phenol and acetone.

Other reactants required are oxygen from air and small amounts of a radical initiator.

Most of the worldwide production of phenol and acetone is now based on this method.

In 2003, nearly 7 billion kg of phenol was produced by the Hock Process.



3.3.1 Technical Description

Benzene and propylene are compressed together to a pressure of 30 standard

atmospheres at 250 C (482 F) in presence of a catalytic Lewis acid. Phosphoric

acid is often favored over aluminium halides. Cumene is formed in the gas-

phase Friedel-Crafts alkylation of benzene by propylene:

Cumene is oxidized in air which removes the tertiary benzylic hydrogen from

cumene and hence forms a cumene radical:



3.2.1 Cumene Chemical Properties

Cumene is a colourless liquid, soluble in alcohol, carbon tetra chloride, ether and

benzene. It is insoluble in water. Cumene is oxidized in air which removes the

tertiary benzylic hydrogen from cumene and hence forms a cumene radical:

This cumene radical then bonds with an oxygen molecule to give cumene

hydroperoxide radical, which in turn forms cumene hydroperoxide (C6H5C(CH3)2-O-O-

H) by abstracting benzylic hydrogen from another cumene molecule.

This latter cumene converts into cumene radical and feeds back into

subsequent chain formations of cumene hydroperoxides. A pressure of 5 atm is used

to ensure that the unstable peroxide is kept in liquid state.



Cumene hydroperoxide is then hydrolysed in an acidic medium (the Hock

rearrangement) to givephenol and acetone. In the first step, the terminal

hydroperoxy oxygen atom is protonated.

This is followed by a step in which the phenyl group migrates from the benzyl

carbon to the adjacent oxygen and a water molecule is lost, producing

a resonance stabilized tertiary carbocation.

The concerted mechanism of this step is similar to the mechanisms of

the Baeyer-Villiger oxidationand also the oxidation step of hydroboration-

oxidation.[6] In 2009, an acidified bentonite clay was proven to be a more economical

catalyst than sulfuric acid as the acid medium.



As shown below, the resulting carbocation is then attacked by water, a proton

is then transferred from the hydroxy oxygen to the ether oxygen, and finally the ion

falls apart into phenol and acetone.

The products are extracted by distillation.

3.3 Chemical Reaction Network

The mechanism of benzene alkylation with propylene involves the protonation of the

catalyst acidic sites [5, 6] leading to isopropylbenzene, and further di-

isopropylbenzenes and tri - isopropylbenzenes. By the isomerization some n -

propylbenzene appears, which is highly undesirable as an impurity. The presence of

stronger acid sites favors the formation of propylene oligomers and other hydrocarbon

species. Therefore, high selectivity of the catalyst is as important as high activity. It is

remarkable that the polyalkylates byproducts can be reconverted to cumene by

reaction with benzene. Below, the chemical reactions of significance are listed:



3.4 Various Processes of Manufacture

Currently almost all cumene is produced commercially by two processes. The first type

is A fixed bed, Kieselguhr supported phosphoric acid catalyst system developed by

UOP (Universal Oil Products Platforming Process). The second type is A homogeneous

AlCl3 and hydrogen chloride catalyst system developed by Monsanto.

3.4.1 UOP Cumene Process

Figure 3.5: PFD for UOP Cumene Process



Propylene feed fresh benzene feed and recycle benzene are charged to the upflow

reactor, which operates at 3-4 Mpa and at 200-260C. The solid phosphoric acid

catalyst provides an essentially complete conversion of propylene on a one-pass basis.

The typical reactor effluent yield contains 94.8 Wt. % cumene and 3.1 Wt. %

of diiso propylbenzene. The remaining 2.1 % is primarily heavy aromatics. This high

yield of cumene is achieved without transalkylation of diiso propylbenzene and is

unique to the solid phosphoric acid catalyst process.

The cumene product is 99.9 Wt. % pure and the heavy aromatics, which have

an octane number of 109, can either be used as high octane gasoline blending

components or combined with additional benzene and sent to a transalkylation section

of the plant where diiso propylbenzene is converted to cumene.

The overall yields of cumene for this process are typically 97-98 Wt. % with

transalkylation and 94-96 Wt. % without transalkylation.

3.4.1.1 Application

To produce high-quality cumene (isopropylbenzene) by alkylating benzene with

propylene (typically renery or chemical Grade) using liquid-phase Q-Max process

based on zeolitic catalyst Technology.



3.4.1.2 Description

Benzene is alkylated to cumene over a zeolite catalyst in a fixed-bed, liquid-phase

reactor. Fresh benzene is combined with recycle benzene and fed to the alkylation

reactor (1). The benzene feed flows in series through the beds, while fresh propylene

feed is distributed equally between the beds. This reaction is highly exothermic, and

heat is removed by recycling a portion of reactor effluent to the reactor inlet and

injecting cooled reactor effluent between the beds.

In the fractionation section, propane that accompanies the propylene feedstock

is recovered as LPG product from the overhead of the depropanizer column (2),

unreacted benzene is recovered from the overhead of the benzene column (4) and

cumene product is taken as overhead from the cumene column (5). Di-

isopropylbenzene (DIPB) is recovered in the overhead of the DIPB column (6) and

recycled to the transalkylation reactor (3) where it is transalkylated with benzene over

a second zeolite catalyst to produce additional cumene. A small quantity of heavy

byproduct is recovered from the bottom of the DIPB column (6) and is typically

blended to fuel oil. The cumene product has a high purity (99.96 99.97 wt%), and

cu

Date post:	15-Oct-2015
Category:	Documents
Upload:	vprasarnth-raaj
View:	1,549 times
Download:	209 times

Petroleum Assignment - UOP Q-Max Cumene Process (FULL)

Documents