University Of Engineering Technology, Lahore and

Department Of chemical Engineering

Title:
Production of Cyclohexanone by Phenol
hydrogenation

Supervisors:
Dr. Saima Yasin
C0-Supervisor:
Mr. Muhammad Sulaiman
Submitted By:
Ahmed Nadeem 2016-CH-213
Umar Zaheer 2016-CH-215
Hassnat Tahir 2016-CH-235
Muhammad Arslan 2016-CH-237
Contents
Tittle:...........................................................................................................................................................3
Objective:....................................................................................................................................................3
Capacity:..................................................................................................................................................3
Introduction to our project:.........................................................................................................................3
Applications Of Cyclohexanone:..............................................................................................................3
Production Methods of Cyclohexanone:.....................................................................................................4
Cyclohexane Oxidation Process:..............................................................................................................4
Catalytic Oxidation:.................................................................................................................................4
Limitations:..............................................................................................................................................4
Non-Catalytic Oxidation:..........................................................................................................................4
Limitations:..............................................................................................................................................5
Phenol Hydrogenation Process:...................................................................................................................5
Advantages:.................................................................................................................................................5
Process Selection:........................................................................................................................................5
Raw Materials:.............................................................................................................................................5
Phenol.....................................................................................................................................................5
Availability of Phenol in Pakistan:............................................................................................................6
Hydrogen.................................................................................................................................................6
Availability of Hydrogen in Pakistan:.......................................................................................................6
Catalyst:...................................................................................................................................................6
Process Flow Diagram and Important Processes Steps:..............................................................................6
Feasibility Analysis:......................................................................................................................................8
Conclusion:................................................................................................................................................10
References:................................................................................................................................................11

Tittle:
Production of Cyclohexanone by Phenol hydrogenation.
Objective:
The objective of this study is to analyze technical, institutional, economical and industrial
aspects of production of cyclohexanone and the usage of cyclohexanone in industries. As well as
 Production of cyclohexanone from phenol hydrogenation
 Design Specifications of Plant with capacity of 25 kg/hr.
 Enhancing yield of this process
Capacity:
We intend to provide design specifications for plant having capacity of 25kg/hr. of cyclohexanone.

Introduction to our project:

Chemical formula of Cyclohexanone is C 6H10O. It is a six-carbon cyclic molecule with the
ketone functional group. It is colorless oily liquid with acetone like smell. Cyclohexanone is
hazardous material. It is less dense than water with a pleasant odor. Flash point of cyclohexanone
is 43.8o and vapors of cyclohexanone are heavier than air. It is used to form caprolactam and
adipic acid which are used to produce nylon 6 and other plastics. Cyclohexanone is used as a
solvent in paints and dyes, coatings, pharmaceuticals, adhesives, fertilizers, soaps, textile,
chemical industries and intermediate. Pakistan is majorly importing cyclohexanone from other
countries like china, USA, India, Hong Kong, South Korea and Denmark. Major importers of
cyclohexanone in Pakistan are Berger Paints limited, Swat Argo Chemical, Al-Mehran
Chemicals, Nimir Resins Limited, Faiz Chemical Industries, Munir Brother, Sheikh Chemical
Corporation, Vibrant Colors and Chemicals and many sub groups.
Applications Of Cyclohexanone:
 Used as a raw material for the manufacturing of caprolactam and adipic acid
 Employed as a solvent and diluent for paints, inks, synthetic resins, fibers & rubbers
 Employed as a degreasing agent
 Employed as an organic solvent
 Cyclohexanone is an important chemical raw material
 Cyclohexanone is the main intermediate in the manufacturing of nylon, caprolactam and
adipic acid
 Cyclohexanone is also an important industrial solvent for paints, especially those
containing nitrocellulose, vinyl chloride polymers and their copolymers or methacrylate
polymer paints
 Excellent solvent for pesticides such as organophosphorus pesticides
 Cyclohexanone is also used as a solvent for dyes, as a viscous solvent for piston-type
aviation lubricating oils,
 Employed as a solvent for greases, waxes, and rubbers
 It is also used as a leveling agent for dyeing and matting, as well
 Used as degreaser for polishing metal, and wood coloring and painting
  Solvents for fibers, resins, rubbers, waxes, shellac and DDT, organic synthesis,
 Cyclohexanone can dissolve many complexes formed by elements and organic reagents,
determine cesium,
 It can extract reagents for rare metals such as uranium, thorium, cobalt, and titanium

Production Methods of Cyclohexanone:

There are two methods to produce cyclohexanone.
 Cyclohexane oxidation process
 Phenol hydrogenation process
Cyclohexane Oxidation Process:
Benzene hydrogenation is first step that gives cyclohexane and this cyclohexane is
oxidized to give cyclohexanone and cyclohexanol, oxidation process might be catalytic or non-
catalytic oxidation.
Catalytic Oxidation:
Cobalt salt is used as a catalyst with temperature, pressure condition of 125 -165 °C and
0.8 – 1.5 MPa for oxidation of liquid phase cyclohexane.

Ni Co

C6H6 + 3H2 → C6H12 + O2 → C6H10O + H2O

Limitations:
This process easily generates number of oxidation by-products thus have low rate of
conversion (<10%) and high selectivity 80%. Safety is another major issue with this process,
cyclohexane with direct air contact may cause explosion. Low conversion process needs a lot of
recovery and recycling of un-reacted cyclohexane from organic waste by-product. Carboxylic
acid is generated because of oxidation which can easily react with catalyst and make carboxylic
cobalt salt, that can have left in equipment and cause clogging, slagging and blockage in pipe
line, valves etc.
Non-Catalytic Oxidation:
Two steps are involved in this process of oxidation, firstly at 160 – 170 °C cyclohexane brings in
contact with air to give cyclohexyl hydro-peroxide then in presence of alkali media decomposing
of cyclohexyl hydro-peroxide occurred to give cyclohexanone and cyclohexanol.
Limitations:
Selectivity of cyclohexanone and cyclohexanol in this process is less, low per pass conversion of
reactant. Energy Consumption is also very high.
Phenol Hydrogenation Process:
Basic reactions for this process is as follows:

C6H6O + 2H2 → C6H10O (1)

C6H10O + H2 → C6H12O (2)

Pure phenol is vaporized to make a one phase (gas phase) reaction and brings in contact with
hydrogen for the hydrogenation of phenol at 150 °C and 1bar because of reaction cyclohexanone
and cyclohexanol (K/A oil) is produced with some un reacted reactant (phenol and hydrogen)
and by-products. Un-reacted reactants are separated and K/A oil is sent to further processing.
K/A oil is mixture of cyclohexanone and cyclohexanol.
Cyclohexanone is now separated from cyclohexanol and dehydrogenation of cyclohexanol will
be carried out at 330 °C and 2.03 bar to give cyclohexanone and hydrogen in another reactor.
Cyclohexanone is separated from hydrogen and send for further processing to enhancing purity.
This reaction is moderately endothermic that’s why temperature and pressure condition are
higher than the hydrogenation step.

Advantages:
Main advantage of this process with these conditions is that yield of cyclohexanone and
cyclohexanol is about 90 – 95% and selectivity is very high however conversion is 90%. No
waste water, waste gas or toxic organic material is emitted to atmosphere which indicates
environmentally friendly process. This process needs less catalyst inventory. Phenol
hydrogenation is best process for production cyclohexanone.

Process Selection:
Phenol hydrogenation process is selected because this process is more efficient and
environment friendly as compared to cyclohexane oxidation process.

Raw Materials:
Phenol
Phenol also named as carbolic acid and is an aromatic compound. Phenol is obtained now
days from petroleum and it is used as an important commodity in chemical industry it is used on
large scale to synthesis plastics and related materials. Phenol is used in production of many
products and chemical like nylon, polycarbonate, epoxies etc.
Phenol is major raw material in production of cyclohexanone and gives better results than
cyclohexane. Phenol is a limiting reactant in this process. After reviewing literature, it indicates
that for production of cyclohexanone, phenol give beneficial results than cyclohexane because
phenol can directly be obtained from petroleum but on the other hand cyclohexane is derived
from benzene and it increases the cost of raw material. Phenol is economical as compared to
cyclohexane.
Availability of Phenol in Pakistan:
Phenol is not available in Pakistan. It is not produced or manufactured in Pakistan; we have to
import phenol from other countries for this process. Import of phenol is more economical than
the import of cyclohexanone.
Hydrogen
Process named as hydrogenation of phenol, for this purpose hydrogen is required in a
large amount. Hydrogen gas is obtained from different methods having different applications.
Hydrogen gas can be produced from different process like steam reforming of natural gas,
biomass treatment, electrolysis of water etc. Mostly industrial hydrogen is produced using steam
reforming of natural gas.
Availability of Hydrogen in Pakistan:
Hydrogen gas is easily available in Pakistan. We can buy it at cheap price from local
manufacturers in Pakistan.
Catalyst:
Various types of catalysts can be used in this process such as platinum, Palladium, nickel
etc. Selection of catalyst depends on the selectivity and conversion rate according to various
temperature and pressure conditions. Platinum and palladium are mostly used for this process
with silica gel bed. Platinum is used in hydrogenation of phenol in micro size particles so that the
surface area and active site of metal exposed to reactants and desired conversion can be
achieved. Palladium based catalysts are more selective but this is exothermic reaction and it can
create hotspot in reactor.

Process Flow Diagram and Important Processes Steps:

Important steps of the process are as follows:
 Mixing and Heating
 Phenol Hydrogenation
 Phenol Recovery
 Hydrogen recovery
 Purification of Cyclohexanone
Suggested block flow diagram for this process are as follows
Mixing and Heating:
Fresh phenol is mixed with recycled phenol that is recovered from phenol recovery
section in a mixer because viscosity of phenol is low and no internal layer bonding is present
between phenol hence greater power mixer cannot be used. Recycle stream from phenol recovery
section containing phenol and very few amounts of cyclohexanol in ppm which is ignored and
assumed that pure phenol is recycled and mixed with fresh phenol. This stream from mixer is
passed through couple of heat exchangers. Temperature of stream raised to meet the reaction
requirements.
Phenol Hydrogenation:
Hydrogen and phenol mixture after heating is supplied to reactor (hydrogenator shell) at specific
reactor condition of 150°. Reactor has almost 90% conversion under specific Condition. As
reaction is exothermic coolant is supplied so that temperature of reactor can be maintained
Couples of heat exchangers are installed to reduce temperature of the stream and to liquefy vapor
for the ease of separation of hydrogen gas.
Phenol Recovery:
Stream containing Phenol and KA-oil is operated through flash evaporator to recover phenol. As
relative volatility and boiling point difference between components is not much greater so
column is operated under vacuum to achieve desired purity of phenol from bottom of column.
While Cyclohexanone in stream is collected all at top of column with cyclohexanol. This is
Multicomponent distillation in which cyclohexanone is non-key component, cyclohexanol is
light key and phenol is heavy key.
Hydrogen recovery
Vertical flash tank is installed for separation of un-reacted hydrogen from produced
liquid (KA-oil). Hydrogen from top of hydrogenator is recycled back to the system and mixed
with fresh hydrogen and supplied to mix with phenol. Liquid stream which contains un-reacted
phenol and KA oil is obtained from bottom of the reactor.

Purification of Cyclohexanone:
Distillate from distillation column after passes through different the heat exchangers. This stream
contains cyclohexanone and cyclohexanol also known as KA-oil is treated with different
processes for purification and separation of cyclohexanone from KA-Oil.

Feasibility Analysis:
Feasibility analysis is used to determine the viability of an idea. It tells us whether we can invest
on this project or not, in some cases, a project may not be doable. Its’ a detailed study related to
the project. A well-designed study should offer a historical background of the business or
project, such as a description of the product or service, accounting statements, details of
operations and management, marketing research and policies, financial data and legal
requirements.
Some of the steps on which feasibility of the process depends are as follows:
• Raw materials availability

• Markets
• Energy availability
• Waste disposal
• Labor supply
• Climate
The project on which we are working is the production of Cyclohexanone. In Pakistan, this plant can ne
industrial revolution and huge success. Because almost all of the cyclohexanone is imported from other
countries at high cost. This plant is feasible because of the major easy access of raw materials and water,
energy availability, suitable climate and good transportation facilities in this whole region.
Raw Materials Availability:
Raw material required for cyclohexanone production is Phenol and hydrogen gas. Phenol
is not available in Pakistan as per our requirements. So, phenol will be imported from foreign
Countries like china etc. using Karachi sea port to meet our requirements. So, raw material will
be easily available via Qassim Port, Karachi. Many industries are producing hydrogen and it is
easily available in Pakistan. Although we have to import phenol but still our process will be
economical.
Markets:
There is a huge market of chemicals in this region mainly Punjab and Sindh. Also, no chemical
industry in Pakistan is producing Cyclohexanone. Almost all of the cyclohexanone is imported
from other countries at very high cost. A lot of local manufacturers will be attracted to this local
made product due to its low price as compared to the price of the imported cyclohexanone.
Climate:
Climate has a special influence on the revenue generation because If the plant is in a cold
climate, costs may be increased due to construction of protective shelters around the equipment.
If the plant is in hot climate, then special cooling tower air-conditioning equipment may
be required. If there is excessive humidity or extremes of hot or cold weather, then it will cause
serious effect on the economic operation of a plant.
The weather in the region remains moderate so it has no special effect on this process.
Waste Disposal:
It is a major issue in any industry because in recent years many legal restrictions have been
placed on the methods for disposing of waste materials from the process industries. So, the site
selected for a plant should have adequate capacity and facilities for correct waste disposal. So,
the permissible tolerance levels for various methods of waste disposal should be considered
carefully, and attention should be given to potential requirement for additional waste treatment
facilities.
Moreover, this process has no special waste which can cause environment pollution.
Cyclohexanol and other byproducts are recycled to increase the yield of the process.

Labor supply:
Labor is an important asset of any industry Pakistan has large population that can work in
industrial environment at low cost. Engineer and lower staff are also available with all expertise
required to run this plant.
Energy Availability:
Availability of the energy at low rates is important for the economics of the process. Pakistan
have covered its energy crisis and enough energy is available for running this process.

Conclusion:
Considering all the factors discussed above this plant is very suitable and feasible in Pakistan.
Method of production selected for this process is successfully conducted in all part of the world.
So, conditions here are very suitable. Above discussion proves that this plant is feasible in
Pakistan.
References:
 https://onlinelibrary.wiley.com/doi/10.1002/cjce.23363
 https://pubs.rsc.org/en/content/articlelanding/2017/gc/c7gc01318c#!divAbstract
 http://www.haofeichem.com/info/chemical-properties-and-uses-of-cyclohexanone-
25015613.html
 https://www.academia.edu/11418858/Phenol_Hydrogenation_to_Cyclohexanone_129_5_
5.1_Basis_of_Design
 https://www.futuremarketinsights.com/reports/cyclohexanone-market
 http://paktradeinfo.com/international-trade/pakistan/import/1/buyername()-sellername()-
itemdesc(cyclohexanone)
 https://www.academia.edu/people/search?
utf8=✓&q=prduction+of+cyclohexanone+from+phenol+hydrogenation