Process Synthesis Tree for production of Cyclohexane

1. Product Definition (Literature Survey)

Figure 1: Structure of Cyclohexane

CAS Number 110-82-7

Chemical Formula C6H12
Molar Mass 84.162 g·mol−1
Appearance Colourless liquid
Density 0.7739 g/ml
Melting Point 6.47 °C (279.62 K)
Normal Boiling Point 80.74 °C (353.89 K)

Cyclohexane is a versatile chemical compound primarily used as a precursor in the production

of nylon. Its main industrial application involves its oxidation to cyclohexanone and
cyclohexanol, which are key intermediates in the manufacture of adipic acid and caprolactam,
essential components for producing nylon-6 and nylon-6,6 polymers. Beyond its critical role
in the nylon industry, cyclohexane also serves as a solvent in chemical synthesis and industrial
processes, providing an effective medium for dissolving resins, waxes, and other chemical
substances. Additionally, due to its relatively low toxicity and high solvency power,
cyclohexane is frequently employed in laboratory settings for organic synthesis and
purification processes. Its wide-ranging applications underscore its importance in both
industrial manufacturing and research contexts. India is one of the largest cyclohexane
exporters in the global market.
2. Methods of Production & Likely Chemistry at work
Route 1: Catalytic Hydrogenation of Benzene

On an industrial scale, cyclohexane is produced by hydrogenation of benzene in the presence

of a Raney nickel or other suitable catalysts. Producers of cyclohexane account for
approximately 11.4% of global demand for benzene.

Route 2: Recovery from petroleum streams by fractionation and extraction.

Cyclohexane is one of components of naphtha, from which it can be extracted by advanced

distillation methods. Distillation is combined with isomerization of methylcyclopentane,
extracted from naphtha by similar methods.

Route 3: Baeyer synthesis by ketonization of pimelic acid.

In 1894, Baeyer synthesized cyclohexane starting with a ketonization of pimelic acid

followed by multiple reductions. (First discovered Lab synthesis route)

Route 4: Perkin / Haworth synthesis via a Wurtz reaction of 1,6-dibromohexane.

Another lab synthesis route.

There are various other routes which mainly utilize derivatives of benzene or cyclohexane.
Eg. From Anisole, diphenyl ether, Bromocyclohexane, bromobenzene etc. The starting
feedstock material for these derivatives is benzene itself. Hence, these routes are not
preferred since we can avoid unnecessary derivatization and directly use Benzene for
cyclohexane production.

Route Selected: Benzene Hydrogenation

Justification and comparison with other routes:

Benzene hydrogenation is the premier method for commercial cyclohexane production due to
its efficiency and product purity. This process achieves approximately 99% conversion of
benzene to cyclohexane, ensuring minimal waste and optimal use of raw materials. The
resulting cyclohexane has a purity level exceeding 99%, essential for high-quality nylon
production. The use of effective catalysts, such as nickel or platinum, enhances reaction rates
and selectivity, further improving yield and reducing costs. Additionally, the process's
scalability and environmental benefits make it the preferred choice for industrial applications.

In case of Route 2, it is less efficient and produces a lower purity product compared to
benzene hydrogenation. The cyclohexane content in naphtha is typically very low, ranging
from 0.5% to 1.0%. Consequently, the recovery process from petroleum streams involves
complex fractionation and extraction steps. The cyclohexane obtained through this method
has a purity of approximately 85%, which is insufficient for high-quality applications like
adipic acid production used in nylon manufacturing. To achieve the necessary purity levels,
further purification processes such as isomerization and heat cracking are required, which add
to the operational costs and complexity of the process. These limitations make naphtha
fractionation a less favorable option compared to the high conversion and purity achieved
through benzene hydrogenation.

Routes 3 and 4 for cyclohexane synthesis, while used in laboratory settings, involve multiple
steps, poor yields, and low purity. They lack scalability and are not suitable for commercial
production due to these limitations. Hence, benzene hydrogenation remains the preferred
industrial method due to its high conversion rate, superior product purity, and economic
viability.
3. Economic Feasibility:
We can estimate the economic potential for the selected route using raw material costs and
current product selling price.

Basis: 1 gmol of Cyclohexane,

Material Price Req. amount Cost

(Rs./Kg) (Rs./gmol) (Rs./gmol of product)
Benzene 91 7.11 1 gmol 7.11
Hydrogen 200 0.4 3 gmol 1.2
Total 8.31

Assumption: 100 % conversion of benzene (in reality it is close to 99%)

Current Cyclohexane price: 105 Rs./kg == 8.82 Rs./gmol

Since, the RM cost is less than the product selling price, we can assume for now this route is
economically feasible.
Price difference: 8.82-8.31= 0.51 Rs./gmol == 5.95 Rs./kg of cyclohexane

4. Material Balance:
The plant capacity I have decided to take is 20 KTPA (kilo tonnes per annum). The plant will
be run in continuous mode with 8000 working hours per year.

Hence,

Production Capacity = 20,000 TPA = 2.5 Tonnes per hour.

kg/hr kmol/hr
Output
Cyclohexane 2500 29.76
Input Required
Benzene 2321.4 29.76
Hydrogen 178.6 89.29

Required amount of catalyst will be calculated based on reaction kinetics and activity.
5. Block Diagram

Feed Preparation:

• Benzene Feedstock

• Hydrogen Feedstock

Hydrogenation Reactor:

• Benzene and hydrogen are fed into the reactor.

• The reaction C6H6+3H2→C6H12C_6H_6 + 3H_2 \rightarrow C_6H_{12}C6H6

+3H2→C6H12 occurs in the presence of a nickel catalyst.

Heat Exchanger:

• The reaction mixture exits the reactor and passes through a heat exchanger to cool the
products.

Gas-Liquid Separator:

• The cooled reaction mixture enters a separator to remove unreacted hydrogen gas,
which is recycled back to the reactor.

Distillation Column:

• The liquid mixture from the separator is fed into a distillation column.

• Cyclohexane is separated from other by-products and impurities.

Cyclohexane Purification:

• The distillate containing cyclohexane is further purified to achieve the required purity
levels.

Storage:

• The purified cyclohexane is stored in tanks for subsequent use or sale.

6. Selection of Technology
The production of cyclohexane through benzene hydrogenation involves several critical
technological choices:

1. Catalyst Selection: Nickel is the most common catalyst for this process, known for
its cost-effectiveness and high activity, achieving over 99% conversion and producing
cyclohexane with high purity.

2. Reactor Design: Fixed-bed reactors are typically used in industry for their efficiency
in continuous operations, although alternative designs like fluidized-bed and
membrane reactors may enhance performance.

3. Operating Conditions: The reaction occurs at elevated temperatures (150-250°C)

and pressures (20-50 bar). Optimizing these conditions can improve yield and
minimize side reactions.

4. Process Flow: Efficient integration of hydrogen supply and recycling unreacted

hydrogen from the gas-liquid separator is essential. Utilizing heat exchangers to
recover energy from the exothermic reaction can further enhance sustainability.

5. Safety and Environmental Considerations: Given the flammability of hydrogen,

strict safety protocols are necessary. Additionally, effective emission control systems
are vital for compliance with environmental regulations.
7. Operational Diagram

8. Equipment selection:

When selecting equipment for cyclohexane production through benzene hydrogenation,

several factors need to be considered for each major component of the system. Below is an
analysis of the equipment typically used in this process:

1. Hydrogenation Reactor:

o Type: Fixed-bed reactors are the most common choice due to their simplicity
and effectiveness in continuous processes. They can efficiently handle large
volumes of feedstock and provide good temperature control.

o Considerations: The catalyst's physical form (e.g., pellets or coated on a

support) and the reactor's ability to manage heat generated by the exothermic
reaction are crucial for maintaining optimal operating conditions. Alternatives
like fluidized-bed reactors may offer better mass transfer and heat
management but can be more complex and costly.
2. Heat Exchanger:

o Type: Shell-and-tube heat exchangers are frequently used in this application.

They are effective for transferring heat between the hydrogenation reactor and
the incoming feedstock or coolant.

o Considerations: The choice of materials (stainless steel, for example) is

important to withstand corrosion and high temperatures. Efficient heat
recovery can reduce energy costs and enhance overall process sustainability.

3. Gas-Liquid Separator:

o Type: Vertical or horizontal separators can be employed to efficiently separate

unreacted hydrogen from the liquid cyclohexane product.

o Considerations: Design features such as inlet devices and baffles are crucial
for minimizing gas retention and enhancing separation efficiency. The
separator must be sized appropriately to handle the expected flow rates.

4. Distillation Column:

o Type: Continuous distillation columns are typically used to purify

cyclohexane from by-products and impurities.

o Considerations: The column design, including the type of packing (e.g.,

structured packing or trays), affects separation efficiency. Proper control
systems for temperature and pressure are also essential for maintaining desired
product specifications.

5. Storage Tanks:

o Type: Atmospheric storage tanks or pressurized vessels may be used,

depending on the handling requirements of the purified cyclohexane.

o Considerations: Materials of construction should be compatible with

cyclohexane to prevent leakage or degradation. Safety measures, including
vapor recovery systems, are also critical to manage flammability risks.
 6. Piping and Instrumentation:

o Type: Piping systems should be designed for the specific conditions of

pressure and temperature encountered in the process, using materials like
carbon steel or stainless steel.

o Considerations: Instrumentation for monitoring pressure, temperature, and

flow rates is crucial for ensuring safe and efficient operation. Advanced
control systems can optimize performance by adjusting parameters in real
time.

9. Process Evaluation
1. Safety Study

1. Process Hazards

• Flammability and Explosion Risks:

o Hydrogen: Hydrogen is highly flammable and poses significant explosion

risks when mixed with air. Any leaks can lead to potentially explosive
mixtures, particularly in confined spaces.

o Benzene: This compound is also flammable and can contribute to fire hazards.
Precautions must be taken to prevent leaks and spills during handling.

• Toxicity:

o Benzene: As a known carcinogen, benzene can pose serious health risks upon
inhalation or skin exposure. Monitoring benzene concentrations in the
workplace and implementing appropriate personal protective equipment (PPE)
and ventilation systems is crucial.

• Reactor Pressure and Temperature Control:

o The process operates at high pressures (20-50 bar) and temperatures (150-
250°C). Maintaining these conditions is critical; failure can lead to equipment
failures or uncontrolled reactions.

o Safety Relief Valves: Properly functioning safety relief valves are essential to
prevent overpressure situations in reactors.
2. Reaction Hazards

• Exothermic Reaction Risks:

o The hydrogenation of benzene is exothermic, releasing heat that, if not

controlled, can lead to runaway reactions, causing thermal hazards and
damaging equipment.

o Heat Management Systems: Effective heat management systems, such as

heat exchangers, are necessary to dissipate excess heat and maintain safe
operating temperatures.

• Side Reactions:

o Side reactions may occur under certain conditions, leading to the formation of
unwanted by-products that can complicate the separation and purification
processes. These by-products can introduce additional hazards and must be
carefully monitored.

2. Controllability study

1. Hydrogenation Reactor

• Control Parameters: Monitor temperature, pressure, and hydrogen flow rate.

• Control Strategies: Advanced methods like model predictive control (MPC)

optimize conditions. Real-time monitoring enables quick adjustments based on feed
composition.

2. Heat Exchanger

• Control Parameters: Focus on temperature differentials and flow rates.

• Control Strategies: PID controllers adjust flow rates to maintain stable temperatures.

3. Gas-Liquid Separator

• Control Parameters: Key parameters include pressure, temperature, and liquid and
gas flow rates.
 • Control Strategies: Level controllers and density measurements enhance separation
efficiency.

4. Distillation Column

• Control Parameters: Monitor top and bottom product compositions and temperature.

• Control Strategies: Online analyzers optimize reflux ratios and reboiler duty to
maintain product quality.

5. Storage Tanks

• Control Parameters: Continuous monitoring of level, pressure, and temperature.

• Control Strategies: Level controllers and pressure relief systems ensure safe storage
conditions.

6. Piping and Instrumentation

• Control Parameters: Monitor flow rates, pressure, and temperature.

• Control Strategies: Flow meters and automated shutoff valves enhance safety in the
system.

3. Economic Evaluation.

Plant capacity: 20,000 TPA

As seen previously,
Cyclohexane price-RM cost = 5.95 Rs./kg of cyclohexane

According to “Encyclopedia of Chemical Processing and Design by John McKetta , the

labour cost and the fixed costs of cyclohexane plant of such capacity are negligible.

Therefore, Estimated annual gross profit = 5.95*20000*1000

= Rs. 11,90,00,000 = Rs. 11.9 Crs/year.

This profit can be considerably increase if instead of buying hydrogen, we produce it in-situ
in the plant itself via SMR (Steam Methane Reforming)

This will lower the cost of hydrogen from 200 Rs./Kg to around 50 Rs./kg.

In conclusion, process is economically viable.