KUWAIT UNIVERSITY
Literature Survey
Phenol Production By Cumene Peroxidation
Group 1
Introduction:
phenol are a manufactured class of weakly acidic compounds that is soluble in water
, they are related to organic compounds , that naturally occur in most of food
production ,also used as a slimicide , disinfectant in medical issues .
Phenols are also called phenolics; they are class of aromatic organic compounds that
consists of one or more of hydroxyl groups that are attached to an aromatic
hydrocarbon group.
Phenol is a benzene cycle derivative, it's the simplest part of the phenolic chemicals,
its chemical formula is C6H5OH, and its structure is a hydroxyl group (-OH) bonded
to phenyl group. Synonyms of phenol include carbolic acid, benzophenol and
hydrobenzene.
It is found Solid in the natural state at a temperature of 25 Celsius, Mild acidity,
Needs handled carefully to avoid burns; it is used in industrial processes since
Extracted directly from crude oil and is considered basic material for the
manufacture of many materials, such as plastics, building materials, medicines and
polymers.
HISTORY:
Phenol was detected the first time in 1834 where it was extracted from tar,
In 1912 was used phenol disinfectant for wounds in medical surgery operations,
Germans used phenol in World War II to kill prisoners by injecting their bodies.
World production and consumption:
Country
phenol capacity in thousands of tons per
year
united states
1430
Japan
1230
Korea
530
Taiwan
380
Saudi Arabia
640
China
200
Italy
480
Brazil
1870
Spain
600
Kuwait
600
France
195
Company
Ineos Phenol
Sunoco
Mitsui
Shell
CEPSA Quimica
Polimeri Europa
FCFC
MtVemon Phenol(sabic)
Kumho
Dow
Taiwan Prosperity
Mitsubishi chemicals
Ghiba Phenol
Georgia Gulf
LG Chem
Chang Chun PC
Rhodia
NOVAPEX
Phenol capacity in thousands of tons
per year
1870
800
750
600
600
480
400
340
330
300
200
250
230
230
200
200
195
180
Bisphenol A accounted for 49% of global phenol consumption in 2010, followed by
phenol-formaldehyde resins at 25%. Bisphenol A and phenol-formaldehyde resins
are produced in all regions.
USES:
Phenol is used in building materials, transportation, detergents and medical products
drops ear, nose,Mouthwash,Aspirin),Phenol prevents to Kabrulaktam for making
nylon,
Mistake contains phenol, a substance important medical; Phenol is used in the
execution
Of cosmetics and sun shields and hair dyes, Phenol is used in cosmetic surgery,
where he Is still dead skin.
Physical and chemical properties :
Oxygen
Molecular weight
32 g/mole
Molecular formula
O2
Boiling/condensation point
-183 °C (-297.4°F)
Melting/freezing point
-218.4 °C (-361.1°F)
Critical temperature
-118.6°C(-181.5°F)
Vapor density
1.105 (air =1)
Specific volume (ft3/lb)
12.0482
Gas density (lb/ft3)
0.083
Cumene
Molecular weight
120.2 g/mole
Color
Clear colorless
Boiling point
152.4°C (306.6°F)
Melting point
Physical state and appearance
Specific gravity
Vapor pressure
Vapor density
Oder threshold
Water/oil dist.coef.
Solubility
-96 °C (-140.8 °F)
liquid
0.862 (water=1)
8mmof Hg (@20°C)
4.41 (Air=1)
1.2ppm
3.7
Very slightly soluble in cold
water
Phenol
Physical state and appearance
Solid
Odor
distinct, aromatic , somewhat sickening sweet
Taste
burning
Molecular weight:
94.11 g/mole
Color:
colorless to light pink
Boiliong point
182 c
Melting point
42 c
Critical temperature
694.2 c
Specific gravity
1.057
Vapor density
3.24
Odor threshold
0.048 ppm
Water /oil dist.coff
1.5
Solubility
easily soluble in cold water . hot water
Acetone:
Physical state and appearance
Liquid.
Odor
Fruity. Mint-like. Fragrant. Ethereal
Taste
Pungent, Sweetish
Molecular weight
58.08 g/mole
Color
colorless
Ph
not available
Boiliong point
56.2 c ( 133.2 f )
Melting point
-95.35 c( -139.6 f)
Critical temperature
235 c ( 455f)
Specific gravity :
0.79 ( water =1 )
Vapor density
2 ( air =1 )
Volatility
not available
Odor threshold
62 ppm
Water /oil dist.coff
-0.2
Lonicity ( in water ) :
not available
Dispersion propertiers
see solubility in water
Solubility
easily soluble in cold water . hot water
Process description:
Phenol production routes:
Phenol can be produced by 3 main routes;
1) Cunene peroxidation process
2) Chlorobenzene – sulfunation process
3) Sulfunation process
In our literature survey we will concentrate on cumene peroxidation process
because it is very well known in which 95% of phenol world production is
manufactured using this route. As for the other two routes we will not consider
them as useful routes for the following reasons:
1) Lower conversion per pass in chlorobenzene – sulfunation process.
2) The sulfunation process requires operating with high temperature which means
more recurring costs as well as using large batch cycles with lower productivity
Cumene peroxidation process:
Cumene production:
Cumene is produced by mixing benzene with propylene in the presence of acid
catalyst. This mixing process is also known as alkylation process. In the alkylation
reaction the most commonly used catalyst is zeolite because it gives 99% yield
cumene
Phenol production:
The production of phenol occurs with two main reactions, the first one is cummene
oxidation to cumene peroxide which is the intermediate product of the reaction.
Fresh cumene is pumped into a drum while recycled cumene is being treated with
water and weak caustic in order to remove organic acids. In addition, cummene from
AMS hydrogenation section is being added to fresh cummene feed as well as the
concentration section and acetone refining section. The treated cumene is combined
with fresh cumene to enter the oxidizer at PH (6-8) and temperature (110°c - 115°c)
with 25% conversion. The lower the temperature of the operating conditions of the
oxidizer the lower the conversion.
Two oxidizers are being used in the oxidation process. then the product which
contains cumene peroxide, water, and unconverted cumene is being cooled before it
is introduced to the charcoal absorbers were spent air is being released and the
remain mixture enters a decanter were the remain cumene is desorbed with low
pressure followed by condensing steam and cumene decantation .next, the decanted
cumene enters a caustic was to treat the cumene with weak caustic before
combining it to the fresh feed.
Concentration section:
Cumene hydro-peroxide (CHP) is concentrated to 75 – 85 wt % before it is
decomposed to phenol and acetone
The concentration section recovers UN reacted cummene. CHP is being concentrated
by vaporizing cumene in a preflash coloumn at low pressure; the 2 columns are
operated under vacuum to minimize the temperature needed to concentrate CHP.
Vacuum can be generated by an ejector system. The concentrate CHP is then
introduced to the decomposition section
Decomposition section:
This section involves the decomposition of concentrated CHP in the presence of the
sulfuric acid catalyst at a medium temperature of 70°c - 80°c
This section provides the plant with high phenol yield and conversion of
dicumylperoxide to AMS with a yield of 90%
Sulfuric acid is injected via injection pumps to provide the catalyst required for CHP
decomposition to phenol and acetone. the effluent from the decomposer is heated
using medium pressure steam such that DMPC ( dimethylphenylcarbinol ) traces are
dehydrated at a very high yield of DCP ( dicumylperoxide ) to AMS (alpha-methylstyrene ) 90% yield is achieved
Neutralization section:
Acid catalyst is added in the decomposition section must be neutralized. This section
is very important to prevent yield loss due to side reaction
Also it's very important to avoid corrosion in the units required. The section is
neutralized by injecting an amount of diamene which does not need to be removed
which means lower capital cost because we don’t need a separator. In addition it
doesn’t require water addition so we don’t have to deal with waste water treatment.
Acetone refining section:
Acetone is one of the main by-products of CHP oxidation. The plant production
economics depends on the production of high quality acetone ( 99% pure) .
Water is injected to the crude acetone column in order to increase the volatility and
maintain the bottom temperatures. The most common impurities are removed from
acetone columns are aldehydes
Most phenol producers use gas chromatography to indentify aldehydes in order to
separate them. Caustic is injected to the finished acetone column to catalyze trace
aldeyhdes. High purity acetone flows by gravitational force as a side stream product
from the acetone fractionation column. Waste water is being separated from
cumene and sent to the sewer while the separated cumene is sent back to the
cumene oxidation section
Structured packing column is used in acetone refining for cost reduction
Phenol fractionation and purification process flow:
Further purification of crude phenol is used to achieve desired purity specifications.
The purpose around this section is to recover cumene and AMS. Chemical agents
are used to remove carbonyl impurities.
A chemical treatment reactor effluent enters the crude phenol column were heavy
components are distilled to the bottom of the column while distilled heavies enter a
stripper for removal of residue byproduct. In the final stripping phenol is controlled
at low pressure in a manner that no high pressure steam is required.
On the other hand, small impurities are removed from the top of the crude phenol
column by pasteurizing section, a side cut is taken from the crude phenol column to
IX resin acid catalyst to catalyze methyl-benzo-furans and residual AMS then enters a
phenol rectifier in order to produce high quality phenol and recycle back heavy
components from the phenol rectifier
Cumene from cumene/AMS column enters a phenol recovery unit were it is washed
with caustic and sent to AMS hydrogenation section
In the AMS caustic wash column, sodium phenate is formed and mixed with
sulphuric acid before entering the PRU separator which separates sprung phenol
from the aques solution. The aques solution is introduced to oil extraction column
and scrubbing column with makeup cumene and caustic to from sodium phenate.
Sodium phenate is recycled back to the PRU separator. Waste water is treated and
pumped to the sewer
AMS hydrogenation section:
This process is made in the presence of a catalyst system that contains lead and
operates at a moderate pressure. This catalyst system operates with a very low
deactivation rate.
In this section AMS is hydrogenated to Cumene and fresh feed of cumene/AMS from
phenol in addition to reactor effluent with hydrogen are mixed together and enter
reactor number 1 were highly exothermic hydrogenation reaction of AMS is
converted to cumene . The effluent is splitted such that it is cooled and recycled back
to reactor 1. The other split enters a second rector to assure full conversion of AMS
to cummene. The effluent of the second reactor is cooled and separated to give off
gas and cummene which is recycled to the oxidation section
Benzene Sulfonation process :
This is one of the routes used in phenol production by converting a benzen cycle to
phenol with presence of inorganic acids and salts .
In this process , we will need different types of seperation such as ; filteration
(pressure filter , centrifuge ) to seperate sodium sulphate and sodium sulphite ,
distillation to seperate phenol from crude phenol , crystallization for seperation and
recovery of sodium sulphite .
Reactions :
1) Sulphonation
- C6H6 + H2SO4 ----> C6H5SO3 + H2O
Benzen reacts with sulphonic acid to benzen sulphonic acid
2) neutrlization :
C6H5SO3 + Na2SO3 -----> C6H5SO3Na
benzen sulphonic acid is neautrlized by adding sodium sulphite to form sodium
sulphonate .
3) Fusion Reaction :
C6H5SO3Na + NaOH ----> C6H5ONa
Sodium benzen sulphonate fused with addition of sodiumhydroxide to produce
sodium phenoxide .
4) Acidification :
C6H5ONa + H2SO4 ----> Na2SO3 + C6H5OH
Sulphuric acid and sodium phenoxide are reacted to produce crude phenol and
soudium sulphite
Process description :
-The process is a batch cycle operated due to slow reaction fusionator (reactor)
sodium benzen sulphonate is fed to fusinator(reactor) made of iron , in presence of
molten caustic soda . the reaction takes from 5 to 6 haours to be achieved . its a
countinuos proccess in loading and unloading .after that , sodium phenoxide that is
produced is fed to an acidifier to produce crude phenol as a product of a reaction of
sodium phenoxide with sulfuric acid and sulphur dioxide . A vacuum distillation is
used to seperate phenol from crude phenol , the remain impurties are sent to a
stripper to remove remaining phenol , crystallizers(seperator) are used to increase
the purity of sodium sulphite that is used in the neutrlizer , the crystals found are
recycled to neutrlizer .
Operation condition :
T = 300
P = 170 atm
Disadvantages :
- The sulfunation process requires operating with high temperature and high
pressure which means more recurring costs .
- large batch cycles with lower productivity.
Chlorobenzne and Caustic process for phenol production:
- For this process we found that 1 ton of phenol we will have approximately the raw
materials needed for this process 0.90 tons of benzen , 0.82 tons of chlorine , 0.67 of
NaoH , 0.51 of HCL .
Route Reactions :
1) Chlorination
C6H6 + Cl2 ---> 850C , Fe- --> C6H5Cl (Chlorobenzene)
2) Causticization
C6H5Cl +NaOH (aq)---> C6H5NaO\
3) Hydrolysis
C6H5NaO + HCl(aq) ---- > C6H5OH + NaCl(aq)
Process description :
in this process , benzen reacts with chlorine in presence of a catalyst which is iron at
a temprature of 85 centigrades to form chlorobenzen in a chlorine tower .
the remained benzen after this section will be recycled , monochlorobenzen will be
pulled out and excess chlorine is used to neuterlize the chlorobenzen , in addition of
10% of caustic soda mixed with chlorobenzen and reacted with it . this reacted
mixture will react with hydrogen and produce water vapors that is removed . the
final product diphenyl oxide is pumped to a heater , then passed to a multi tube
reactor to achieve a custicization reaction that occurs at 425 centigrades and a
pressure of 350 atm , then passed to a neutrlizer .
then, phenol is found by hydrolysis with HCL that occurs at the neuterlizer , in the
neutrlizer the diphenyloxide is concentrated to form phenol and sodium chloride
(salt ) which represents a side product of the process , sodiumchloride is seperated
and sent to an electrolysis unit , upper streams sends the remained to a vacuum
distillation and phenol is stripped out .
- 95% of diphenyloxide is removed to recycle then a small amount of phenol yeild .
Operating conditions :
T = 425 c
P = 350 atm
Disadvantages :
- its not a highly recomended because HCL corrosion in chlorobenzen plant section.
- High pressure vessel design for the causticization reactor.
- High cost with low profits campared with other routes .
Economic analysis:
C + O2-------------> P + A
# of mole
Mwt(lb/lbmole)
weight(lb)
Price($/lb)
weigth/weight
P
C
1
120.2
120.2
0.54
1.277
O2
1
32
32
0
0.34
Profit = (0.617*0.82)+(0.9*1) – (0.34*0) – (0.54*1.277)
= 0.71636 $/lb P
0.71636 $/lb P * (200*10^6 )*0.9
= 128,944,800 $/yr
Profit = 128,944,800 $/yr
P
1
94.11
94.11
0.9
1
A
1
58.08
58.08
0.82
0.617
Conclusion:
The process that we have chosen to explain about in detail is the cumene
peroxidation reaction because it is very well known and produces high purity, high
yield phenol with a valuable by product acetone, unlike other routes which involves
dealing with corrosive and less valuable materials
Recommended flow sheet:
It is a combination of zoomed in flow sheets from Sunoco Company that are used in
this literature survey due to the presence of the detailed process of phenol
production .
patents:
1) Patent application title: Process for Producing Phenol
Inventors: John S. Buchanan (Lambertville, NJ, US) Jon E. Stanat (Westhampton
Beach, NY, US) Tan-Jen Chen (Kingwood, TX, US) Jihad M. Dakka (Whitehouse
Station, NJ, US) James R. Lattner (Laporte, TX, US) James R. Lattner (Laporte, TX,
US)
IPC8 Class: AC07C3708FI
USPC Class: 568798
Class name: Benzene ring containing phenols (h of -oh may be replaced by a group
ia or iia light metal) preparing by cleavage of hydroperoxide or other peroxide
Publication date: 2011-05-05
Patent application number: 20110105805
2) patent number : 4,358,618
United states patent
Inventors : stylanios sifnoids Madison ; allen A.Tunick , botoni , fred w koff long
valley all of NJ
Assignee : allied corporation morrice, township , morris countey , NJ
Appl NO : 276,233
Filled :22 june 1988
References:
http://en.wikipedia.org/wiki/Phenol
http://enggyd.blogspot.com/2010/09/cholorobenzene-caustic-process-for.html
http://enggyd.blogspot.com/2010/07/phenol-manufacturing-process.html
Industrial catalytic process – phenol production
http://Icis.com
http://www.ihs.com/products/chemical/planning/ceh/phenol.aspx