PROCESS 3 (Chlorobenzene and Caustic Process)

Technological Institute of the Philippines
PROCESS 3
PRODUCTION OF PHENOL VIA
CHLOROBENZENE AND CAUSTIC
PROCESS
PROCESS 3
PRODUCTION OF PHENOL VIA CHLOROBENZENE AND
CAUSTIC PROCESS
I. INTRODUCTION
Phenol is one of the major raw materials in producing Bis-Phenol A which is
used in manufacturing plastics and resins. In this process, the percent yield of
phenol is up to 95%, but is economically not attractive. The major raw materials
involved in this process are Benzene, Chlorine, Sodium Hydroxide and
Hydrochloric Acid.
II. REACTION MECHANISM
Three reactions are present in the process such as:
1. Chlorination
` C6H6 + Cl2 85oC, FeCl3 C6H5Cl + HCl
2. Causticization
C6H5Cl +NaOH (aq) C6H5NaO
3. Hydrolysis
C6H5NaO + HCl(aq) C6H5OH + NaCl(aq)

Figure 3.1 Overall Reaction for Chlorobenzene and Caustic Process
III. PROCESS DESCRIPTION
Chlorination
Liquid benzene is sent to the spray column and is dried using 36%
hydrochloric acid as a drying agent. Benzene which is in dry state is reacted with
chlorine at the presence of the catalyst iron chloride at about 85 deg centigrade
temperature to form Chlorobenzene in the bubble column reactor.
Causticization
After the liquid-liquid reaction, unconverted benzene is recycled and
monochlorobenzene is withdrawn all excess chlorine is used in neutralizer and
about 10% solution of dilute caustic soda is mixed with Chlorobenzene which is
reacted with caustic solution where chlorine present at the benzene ring is reacted
with hydrogen and produce water vapors which are removed a tail gas.
The resulting product diphenyl oxide is pumped to the preheater and then
passed to multi-tube reactor where causticization reaction occurs at the
parameters 425 deg centigrade and 350 atm pressure, then the reacted mixture is
passed to the neutralizer through the effluent heat exchangers.
Hydrolysis
Phenol is obtained from hydrolysis occurs at the neutralizer where reaction
with concentrated hydrochloric acid take place to form phenol and sodium
chloride. Sodium chloride is formed as a side product, this salt is separated and
send to electrolysis.
Upstream from the separator is sent to vacuum distillation column together
with the recycle and is preheated to 180 deg centigrade. The phenol in vapor
phase is then condensed and is stripped out as the distillate. About 95% yield is
obtained and diphenyl oxide is removed from the bottom of the column as a
byproduct.
Crystallization
The boiling liquid phenol at 180 deg centigrade is fed to the crystallizer
operating at 31 deg centigrade. The sudden drop in temperature caused the liquid
phenol to crystallize having a purity of 99.99%. The mother liquor is separated
using a centrifuge and is mixed in the mixer before recycling back to the
distillation column.
Fig. 3.2 Process Flow Diagram for the Production of Phenol Via Chlorobenzene and Caustic Process
IV. EQUIPMENT UTILIZED
Table 3.1 Major Equipment for Chlorobenzene and Caustic Process
TAG
EQUIPMENT
NUMBER
1 ST-101 Benzene Storage Tank
2 ST-102 Chlorine Gas Storage Tank
3 ST-103 Iron Chloride Storage Tank
4 ST-104 Sodium Hydroxide Storage Tank
5 ST-105 Hydrochloric Acid Storage Tank
6 ST-106 Sodium Chloride Storage Tank
7 ST-107 Diphenyl Oxide Storage Tank
8 ST-201 Phenol Crystals Storage Tank
9 SC-101 Spray Column
10 R-101 Bubble Column Reactor
11 R-102 Multitube Reactor
12 M-101 Mixer 1
13 M-102 Mixer 2
14 N-101 Neutralizer
15 GS-101 Gravity Settler
16 D-101 Vacuum Distillation Column

17 CT-101 Crystallizer
18 C-101 Centrifuge
19 CV-101 Conveyer
20 H-101 Preheater 1
21 H-102 Preheater 2
V. RAW MATERIALS
BENZENE
Benzene is an aromatic hydrocarbon extracted from cracked gasoline, etc.
It is used as a raw material for styrene, phenol, cyclohexane, and various other
chemicals. It is also used as a solvent. For consumer products where benzene is
used as a building block or intermediate, the benzene is typically fully reacted in
a closed system, with little to no benzene remaining in the finished consumer
product. Benzene is naturally found in crude oil.
Figure 3.3 Benzene Storage Containers

Source: Hefei TNJ Chemical Industry Co., Ltd.
Benzene is commercially obtained primarily from pyrolysis gasoline coproduced
in the steam cracking of naphtha, gasoil or condensates to make olefins.
CHLORINE
Chlorine, along with its important by-product, sodium hydroxide, is
produced from the readily available starting material, rock salt (sodium
chloride). The largest use is in the manufacture of poly(chloroethene), PVC,
other major polymers produced using chlorine include the polyurethanes.
Chlorine is well known for its use in sterilizing drinking water and its application
in swimming pool water.
However, most chlorine is used in the chemical industry in the
manufacture of other products. Sometimes chlorine is in the product molecule
but on other occasions it is used to produce intermediates in the manufacture of
products that do not contain chlorine and the element is recycled.
Figure 3.4 One Ton of Chlorine Container

Source: Indian Springs Manufacturing
Most chlorine is produced on the site on which it is going to be
used, however, some chlorine needs to be transported for example, when it is to
be used to purify water. For this, the chlorine is dried by passing it through
concentrated sulfuric acid and then compressed and liquefied into cylinders,
ready for transportation.
SODIUM HYDROXIDE
Sodium hydroxide (caustic soda) is a clear, slippery, and strong basic
chemical that is a co-product from the manufacture of chlorine using a solution
of the readily available raw material, rock salt (sodium chloride).
These factors contribute to it being the cheapest and most widely used
strong alkali. Another major use of sodium hydroxide is in the manufacture of
paper from wood. In the most used process, the Kraft process, wood is treated
with a solution containing a mixture of sodium sulfide and sodium hydroxide.
Another major use of sodium hydroxide is in the manufacture of paper from
wood.
Figure 3.5 Container of NaOH Solution

Source: Bidspotter
HYDROCHLORIC ACID
Hydrochloric acid or muriatic acid is a colorless inorganic chemical
system with the formula H. O: HCl. Hydrochloric acid has a distinctive pungent
smell. It is classified as strongly acidic and can attack the skin over a wide
composition range, since the hydrogen chloride completely dissociates in
aqueous solution. Hydrochloric acid is a multipurpose raw material used in many
industrial applications. It is used not only in the pulp and paper industry but also
in chemical, metal and food industries. Applications for hydrochloric acid are,
among others, pH adjustment, production of chloride salts, surface treatment of
metals and recovery of ion exchangers.
Figure 3.6 Container of Hydrochloric Acid

Source: IndiaMART
VI. SUSTAINABILITY
AVAILABILITY OF RAW MATERIALS
The raw materials of phenol production using chlorobenzene – caustic
process is benzene, chlorine, sodium hydroxide and hydrochloric acid. Benzene
is not locally available in the Philippines. However, neighboring countries like
China manufactures this raw material with supply ability in tonnage. While, the
Mabuhay Vinyl Corporation is the leading manufacturer of chlorine, sodium
hydroxide and hydrochloric acid in the Philippines.
Table 3.2 Suppliers of Raw Materials for the Sulfur Trioxide Process
Raw material Supplier

Hebei Crovell Biotech Co., Ltd.
Address: No.66,Yuhua West
Road,Shijiazhuang,Hebei,China
Website: http://www.crovellbio.com/
Landline: 0311-66562153
Benzene
Distance from plant:
JG Summit Olfeins Corporation
Address: Brgy. Simlong, Batangas City
Landline: + 63 43 740 5600

Chlorine Mabuhay Vinyl Corporation
Address: Iligan City, Lanao del Norte
Website: www.mvc.com.ph
Landline: 817-8971 to 76
Sodium Hydroxide Mabuhay Vinyl Corporation
International Chemical Industries, Inc.
Address: Km 32 McArthur Highway Bo.
Tuktukan, Guiguinto, Bulacan
Website: www.inchem.com.ph
Landline: 044-7940444 to 45
Hydrochloric Acid Mabuhay Vinyl Corporation

International Chemical Industries, Inc.
Address: Km 32 McArthur Highway Bo.
Tuktukan, Guiguinto, Bulacan
Website: www.inchem.com.ph
Landline: 044-7940444 to 45
DEMAND AND SUPPLY OF RAW MATERIALS
BENZENE
The rapidly growing industries such as packaging, construction, bulk
chemicals & materials, automotive, textiles and building & construction have
substantially driven the applications for the benzene derivatives globally
influencing the benzene market growth. Rising population in tandem with the
increase in disposable incomes has led to growth of many consumer products and
bulk materials. Low cost of the feedstock and economical commodity product
prices have also contributed to the higher consumption of benzene derivatives.
Asia Pacific is the largest regional market for the benzene market due to
high consumption in China. Despite a gradually slowing economy, China has
witnessed all the additional benzene requirements in the past five years (2012-
2017). The consumption has shifted from North America and Western Europe
towards Asia and Middle East over the past decade. (Heraldkeeper via
COMTEX, 2019)
The global benzene market comprises of large number of international
and domestic producers. Global benzene industry has witnessed a shift in
competitive landscape towards closer proximity of the refineries. Some of the
major benzene market players include Sinopec, BASF, China National Petroleum
Corporation, Saudi Basic Industries Corporation, Dow DuPont, ExxonMobil
Corporation, and Royal Dutch Shell plc.
Figure 3.7 World Consumption of Benzene 2018

Source: IHS Markit
Global consumption of benzene will continue to grow at an average
annual growth rate of 2.9% during 2018–23, driven primarily by the developing
markets in Asia, particularly China. Benzene consumption and growth will vary
by region, based on the development of downstream derivative capacity.

The global benzene market comprises of large number of international
and domestic producers. Global benzene industry has witnessed a shift in
competitive landscape towards closer proximity of the refineries. Some of the
major benzene market players include Sinopec, BASF, China National Petroleum
Corporation, Saudi Basic Industries Corporation, Dow DuPont, ExxonMobil
Corporation, and Royal Dutch Shell plc.
CHLORINE
The market for chlorine is expected to register a CAGR of more than
4.5%, during the forecast period. Major factors driving the market studied are the
rising demand from the pharmaceutical and agrochemical industries. However,
stringent government regulations in Europe is expected to hinder the growth of
the market studied. The Asia-Pacific region dominated the global market share.
With growing urbanization and increasing need for fresh water in countries, such
as China and India, the usage of chlorine is increasing in the region.
Figure 3.8 Chlorine Market Growth Rate by Region 2019-2024

Source: Mordor Intelligence
The global chlorine market size exceeded 70 million tons in 2015. The
global industry has experienced a rapid growth in the last few years due to
growing demand for chlorine derivatives from various end-use industries such
as water, pharmaceutical, cosmetic, plastic, food processing, adhesives, paints
& coatings, etc.
Figure 3.9 US Chlorine Market Size by Application 2019-2024

Source: Grand View Research

SODIUM HYDROXIDE
China is the largest producer and consumer of sodium hydroxide, driven
by its status as the workshop of the world. Currently the sodium hydroxide in
China is being excess of production capacity and the government and the top
players are thinking to curb overcapacity in chlor-alkali. In future, China will
remain its existing status and will have greater influence on global sodium
hydroxide supply and demand. There are lots of producers in China, but most of
them are small and medium-sized producers and supply the low-end price, low
price and fierce competition.
Fortunately, in the Philippines, the top manufacturer Caustic Soda is the
Mabuhay Vinyl Corporation. It is the lone chlor-alkali producer in the Philippines
and it produces the highest concentration of sodium hydroxide, at 50%
concentration and at large quantities. The demand for the chlor-alkali products
such as sodium hydroxide is high due to its wide variety of industrial applications,
such as in the manufacture of pulp and paper, textiles, bio-diesel, soaps and
detergents. However, sustainability is expected considering the capacity of the
existing manufacturing plant locally and the availability of trading companies like
International Chemical Industries and overcapacity of the neighbor country like
China.

HYDROCHLORIC ACID
Hydrochloric acid is an integral part of the worldwide chlorine industry.
Most of the HCl produced in the United States, Western Europe and Japan is
generated as a by/product in the manufacture of a wide variety of organic
chemicals via chlorination reactions. This supply depends largely on demand for
the primary products.
A significant amount of by-product HCl is generated when ethylene
dichloride (EDC) is cracked to make vinyl chloride monomer (VCM). This HCl
is usually recycled back to the EDC reactor for additional oxychlorination and
for the most part does not enter the commercial market. Similarly, most of the
HCl generated in the production of chlorinated C1s (primarily methylene
chloride and chloroform) is recycled to produce additional methyl chloride.
Figure 3.12 World Consumption of Hydrochloric Acid 2018

Source: IHS Markit
About 40 processes generate HCl as a coproduct and about 110 chemical
manufacturing processes utilize hydrochloric acid as a raw material. Globally,
nearly 37% of all HCl consumption is to produce EDC, and 61% is used in the
production of organic compounds, most of which is captive consumption. The
remaining consumption is in several inorganic or merchant applications.
Figure 3.13 Global Hydrochloric Acid Market Share by 2018

Source: Market Research Future
Asia-Pacific is estimated to have dominated the global hydrochloric acid
market, with China, India and ASEAN countries being the prominent markets in
the region. The hydrochloric acid market in Asia-Pacific is expected to be the
fastest-growing during the forecast period owing to increasing manufacturing
activities, growing population and developing industries such as food, chemical,
and textile in India and China. North America is expected to be the second-largest
market for hydrochloric acid. The North America Market is expected to witness
moderate growth during the forecast period this growth can be attributed to
increasing investment in hydraulic fracturing activities, growing construction
industry, and increasing investment in the pharmaceuticals industry.
Asia Pacific was the market leader in HCl consumption in 2013 owing to
industrial development in India, Indonesia and China. Middle East, Canada,
Indonesia and China are anticipated to witness the fastest growth on account of
growing oil & gas industry over the forecast period. Major HCl end-use includes ore
processing, calcium chloride & ethyl dichloride production. Additionally, niche
applications of HCl include use in leather, dyes and pigments. HCl is produced by
four basic methods including the combination of hydrogen and chlorine; the
chlorination of organic chemicals; the salt-sulfuric acid production process and as a
co-product during silica manufacturing.

VII. PLANT ECONOMY
The total capital investment and the annual production rate calculations to
produce Phenol via Chlorobenzene and Caustic process are shown in this
section.
RAW MATERIAL COST
Table 3.3 Price of Raw Materials in Process
Raw Material Price (PHP Per Metric Ton)

Benzene 56,131.24
Chlorine 12,500.00
Sodium Hydroxide 20, 411.36
Hydrochloric Acid 13,000.00
TOTAL 87,768.85
Source: ALIBABA
EQUIPMENT COST
Estimated fixed capital cost to produce Phenol via Chlorobenzene and Caustic
process is calculated using the Lang Method, factor from Perry’s Chemical
Engineers’ Handbook 8th Ed.
Table 3.4 Lang Factor’s (Green & Perry, 2008)
Type of Plant Fixed Capital Total Capital

Investment Investment
Solid Processing 4.0 4.7
Solid-Fluid Processing 4.3 5.0
Fluid Processing 5.0 6.0
Source: M. S. Peters, K. D. Timmerhaus, and R. West, Plant Design and
Economics for Chemical Engineers, 5th ed., McGraw-Hill, New York, 2004.
Formula for the computation of Fixed Capital Cost (FCC) was taken from
Chemical Engineering Design Volume 6 by Coulson and Richardson:
Cf = fL Ce (Equation 1)
Where:
Cf = Fixed Capital Cost
fL = total delivered cost of all major equipment items
Ce = the “Lang Factor” which depends on the type of process
Assuming the equipment delivery charge is 5% of the purchased equipment
cost. Thus,
Ce = 1.05(Cost per unit) (Equation 2)
Table 3.5 Cost of Equipment for Chlorobenzene and Caustic Process

Technique
PURCHASING DEC = PC x PCE = DEC x

EQUIPMENT QUANTITY
COST 1.05 FACTOR
Storage Tank
410,000.00 7.00 430,500.00 15,067,500.00
(Carbon Steel)
Spray Tower 300,000.00 1.00 315,000.00 1,575,000.00

Gas Storage
1,225,000.00 1.00 1,286,250.00 6,431,250.00
Tank
Bubble
Column 5,200,000.00 1.00 5,460,000.00 27,300,000.00
Reactor
Mixer 3,411,030.00 2.00 3,581,581.50 35,815,815.00
Causticization
Multi-tube 8,250,000.00 1.00 8,662,500.00 43,312,500.00
Reactor
Neutralizer 1,300,000.00 1.00 1,365,000.00 6,825,000.00
Gravity Settler 1,515,000.00 1.00 1,590,750.00 7,953,750.00
Vacuum
1,309,250.00 1.00 1,374,712.50 6,873,562.50
Distillation
Crystallizer 2,125,000.00 1.00 2,231,250.00 11,156,250.00
Centrifuge 1,425,000.00 1.00 1,496,250.00 7,481,250.00
Conveyor 250,000.00 1.00 262,500.00 1,312,500.00
Compressor 200,000.00 1.00 210,000.00 1,050,000.00
Pump 43,769.00 8.00 45,957.45 1,838,298.00
Condenser 205,500.00 1.00 215,775.00 1,078,875.00
Pre-heater 431,715.00 2.00 453,300.75 4,533,007.50
TOTAL 27,601,264.00 28,981,327.20 179,604,558.00
Source: ALIBABA
PROJECT COST
The fixed capital cost of a plant required to produce Phenol by
Chlorobenzene and Caustic Process is calculated using Table 4 from Chemical
Engineering Design Volume 6 by Coulson and Richardson. The method depends
on the type of processing per equipment.
Table 3.6 Factors for Estimation of Project Fixed Capital Cost for
Chlorobenzene and Caustic process
PROCESS TYPE
ITEM FLUIDS-
FLUIDS SOLIDS
SOLIDS
1. Major Equipment, total
PCE PCE PCE
purchase cost
f1 Equipment Erection 0.4 0.45 0.50
f2 Piping 0.70 0.70 0.70
f3 Instrumentation 0.20 0.15 0.10
f4 Electrical 0.10 0.10 0.10
f5 Buildings, process 0.15 0.10 0.05
*f6 Utilities 0.50 0.45 0.25
* f7 Storages 0.15 0.20 0.25
* f8 Site Development 0.05 0.05 0.05
* f9 Ancillary Building 0.15 0.20 0.30
2. Total physical plant cost

(PPC)
3.40 3.15 2.80
PPC=PCE(1+ f1+...+f9)= PCE
x
f10 Design and Engineering 0.30 0.25 0.20
f11 Contractor’s Fee 0.05 0.05 0.05
f12 Contingency 0.10 0.10 0.10
Fixed Capital = PPC (1 + f10 +
1.45 1.40 1.35
f11 + f12)
Source: Sinnot R.K. (2005)
PHYSICAL PLANT COST (PCC)
Total Physical Plant Cost (PPC)

Total Physical Plant Cost = PCE (1 + f1 + f2 + f3 + f4 + f5 + f6 + f7 + f8 + f9)
PPC = ₱ 179,604,558.00 (1 + 0.45 + 0.70 + 0.15 + 0.10 + 0.10 + 0.45 + 0.20 +
0.05 + 0.20)
PPC = ₱ 610,655,497.20
Fixed Capital Cost (FCC)

Fixed Capital Cost = PPC (1 + f10 + f11 + f12)
FCC = ₱610,655,497.20 (1 + 0. + 0. + 0.)
FCC = ₱ 854,917,696.08
Working Capital Cost (WCC)

Working Capital Cost = FCC (0.05)
WCC = ₱ 854,917,696.08 (0.05)
WCC = ₱ 42,745,884.80
Total Capital Investment (TCI)

Total Capital Investment = FCC + WCC
TCI = ₱ 854,917,696.08 + ₱ ₱ 42,745,884.80
TCI = ₱ 897,663,580.88
Fixed Costs:
Maintenance Cost = (0.10)(FCC)
Maintenance Cost = (0.10)( ₱ 854,917,696.08)
Maintenance Cost = ₱ 85,491,769.61
Operating Labor Cost (OLC):
For a plant capacity of 10 MT per day, for an average condition plant, the
estimated operating labor requirement is employee hours/day/processing step.
Considering a 330 days annual operation and 3 processing steps, the estimated
operating labor requirement was estimated using figure 3.14.
Figure 3.14 Operating Labor Requirements for Chemical Process Industries

(Peters & Timmerhaus, 1991)
Table 3.7 Latest Wage Orders and Implementing Rules Issued by the
Regional Boards as of August 2018 (Department of Labor and
Employment 2018)
INDICATOR SECTOR
NON-AGRICULTURE AGRICULTURE
Region III ₱ 400.00 ₱ 370.00 ₱ 354.00

Source: Department of Labor and Employment (2019)
Calculating for the operating labor costs using the data for manpower:
Operating labor cost =
30 𝑒𝑚𝑝𝑙𝑜𝑦𝑒𝑒 − ℎ𝑜𝑢𝑟𝑠 330 𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑑𝑎𝑦𝑠 𝑃ℎ𝑝 400
( )( )( )
𝑑𝑎𝑦𝑠 − 𝑝𝑟𝑜𝑐𝑒𝑠𝑠𝑖𝑛𝑔 𝑠𝑡𝑒𝑝 𝑦𝑒𝑎𝑟 𝑒𝑚𝑝𝑙𝑜𝑦𝑒𝑒 − 8 ℎ𝑜𝑢𝑟𝑠
(3 𝑝𝑟𝑜𝑐𝑒𝑠𝑠𝑖𝑛𝑔 𝑠𝑡𝑒𝑝𝑠)(1 𝑦𝑒𝑎𝑟 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑜𝑛)

Operating Labor Cost = ₱ 1,485,000.00
Laboratory Cost:
Laboratory cost includes the laboratory analyses required for process
monitoring and quality control. A rough estimate of the cost can be taken as
twenty to thirty percent of the operating labor cost of two to four percent of
thetotal production cost (Coulson, 2005). For the computation of the laboratory
cost, the average percentage will be used. Therefore:
Laboratory Cost = (0.25) (OLC)

Laboratory Cost = (0.25) (₱ 1,485,000.00)
Laboratory Cost = ₱ 371,250.00
Supervision Cost:
Supervision involves the whole management that has direct association
in running the plant. The number of employees needed depends on the size of the
plant and the nature of the process. A typical management team for a unit would
consist of four to five shift foremen, a general foreman, and an area supervisor
and his assistant. A rough estimate of the supervision cost can be taken as twenty
percent of the operating labor cost (Coulson, 2005). Therefore:
Supervision Cost = (0.20) (OLC)

Supervision Cost = (0.20) (₱ 1,485,000.00)
Supervision Cost = ₱ 297,000.00
Plant Overheads:
This section includes the cost for general management, plant security,
medical, canteen, general clerical staff and safety. A rough estimate of the plant
overheads cost can be taken as fifty to one hundred percent of the operating labor
cost. Therefore:
Plant Overheads = (0.50) (OLC)

Plant Overheads = (0.50) ( ₱1,485,000.00)
Plant Overheads = ₱ 742,500.00
Capital Charges:
A rough estimate of the capital charge cost can be taken as ten percent
of the fixed capital cost. Therefore:
Capital Charges = (0.10) (FCC)

Capital Charges = (0.10) (₱ 854,917,696.08)
Capital Charges = ₱ 85,491,769.61
Local Taxes:
A rough estimate of the local taxes can be taken as one to two percent of
the fixed capital cost. For the computation of local taxes, the average value will
be used. Therefore:
Local Taxes = (0.02) (FCC)

Local Taxes = (0.02) (₱ 854,917,696.08)
Local Taxes = ₱ 17, 098,353.92
Insurance:
A rough estimate of the insurance cost can be taken as one to two percent
of the fixed capital cost. For the computation of insurance cost, the average value
will be used. Therefore:
Insurance = (0.015) (FCC)

Insurance = (0.015) ( ₱ 854,917,696.08)
Insurance = ₱ 12,823,765.44
License Fee/Royalty Fees:

A rough estimate of the license fee/royalty fees can be taken as one to two
percent of the fixed capital cost. For the computation of license fee/royalty fees
the average value will be used. Therefore:
License Fee or Royalty Fees = (0.015) (FCC)

License Fee or Royalty Fees = (0.015) (₱ 854,917,696.08)
License Fee or Royalty Fees = ₱ 12,823,765.44
Fixed Costs = MC + OLC + LC + SC + PO + CC + LT + I + LF
Fixed Costs = 85,491,769.61 + 1485000 + 371250 + 297000 + 742500 +
85,491,769.61 + 17,098,353.92 + 12,823,765.44 + 12,823,765.44
Fixed Costs = ₱ 216,625,174.02
Variable Costs
Miscellaneous Operating Materials (MOM):
MOM = (0.10) (Maintenance Cost)
MOM = (0.10) (₱ 85,491,769.61)
MOM = ₱ 8,549,176.96
Variable Costs = MOM
Variable Costs = ₱ 8,549,176.96

Direct Production Cost (DPC):
DPC = Variable Costs + Fixed Costs
DPC = ₱ 8,549,176.96 + ₱ 216,625,174.02

DPC = ₱ 225,174,350.98
Indirect Production Cost (IPC):
Sale Expense:
Sale Expense = 0.20 (Variable Cost + Fixed Costs)
Sale Expense = 0.2(₱ 8,549,176.96 + ₱ 216,625,174.02)
Sale Expense = ₱ 45,034,870.20
General Overheads:
General Overheads = 0.30(Variable Cost + Fixed Cost)
General Overheads = 0.30(₱ 8,549,176.96 + ₱ 216,625,174.02)
General Overheads = ₱ 67,552,305.29
IPC = Sales Expense + General Overheads
IPC = ₱ 45,034,870.20 + ₱ 67,552,305.29
IPC = ₱ 112,587,175.49
Annual Production Cost:

APC = IPC + DPC
APC = ₱ 112,587,175.49 + ₱ 225,174,350.98
APC = ₱ 337,761,526.47 / year
Production Cost:
𝐴𝑃𝐶
Production Cost =
(𝑃𝑙𝑎𝑛𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦/𝐷𝑎𝑦)(330 𝑊𝑜𝑟𝑘𝑖𝑛𝑔 𝐷𝑎𝑦𝑠/𝑦𝑒𝑎𝑟)
₱ 514,940,986.97 /year
Production Cost =
MT days
(10 ) (330 working )
day year
Production Cost = ₱ 102,351.98 / MT
The annual production cost required for the plant to 10 MT/day of
Phenol Crystals using chlorobenzene and caustic process is estimated as
₱337,761,526.47/year. Cost of the amounts were allotted for direct production
cost. The estimates were made without the utilities costs that account for the
₱102,351.98 / MT annual production rate.

VIII. MANUFACTURABILITY
PURITY
The phenol crystals obtained from the chlorobenzene and caustic process has a
purity of 99.99%
YIELD
The phenol crystals obtained from the chlorobenzene and caustic process has a
product yield of 95%.
BY - PRODUCTS
The by-product of the phenol crystals obtained from the chlorobenzene and
caustic process is Diphenyl Oxide.
PROCESS USAGE
The production of phenol crystals through chlorobenzene and caustic process is
being used by different plants around the world such as:
• Dow Chemical Corporation

IX. SAFETY
Table 3.8 Equipment Parameters for Chlorobenzene and Caustic Process
EQUIPMENT PARAMETERS
Benzene Storage Tank T = 30 ℃; P = 1 atm
Chlorine Gas Storage Tank T = 30 ℃
Iron Chloride Storage Tank T = 30 ℃; P = 1 atm
Sodium Hydroxide Storage Tank T = 30 ℃; P = 1 atm
Hydrochloric Acid Storage Tank T = 30 ℃; P = 1 atm
Sodium Chloride Storage Tank T = 30 ℃; P = 1 atm
Diphenyl Oxide Storage Tank T = 30 ℃; P = 1 atm
Phenol Crystals Storage Tank T = 30 ℃; P = 1 atm
Spray Column T = 30 ℃; P = 1 atm
Bubble Column Reactor T = 85 ℃; P = 5 atm
Multitube Reactor T = 425 ℃; P = 350 atm
Mixer 1 T = 85 ℃; P = 1 atm
Mixer 2 T = 30 ℃; P = 1 atm
Neutralizer T = 30℃; P = 1 atm
Gravity Settler T = 30℃
Vacuum Distillation Column T = ℃; P = atm
Crystallizer T = 31 ℃; P = 1 atm
Centrifuge T = 30 ℃; P = 1 atm
Conveyer T = 30℃; P = 1 atm
Preheater 1 T = 425℃; P = 1 atm
Preheater 2 T = 180℃; P = 1 atm
Equipment Safety
Multiple Tube Reactor has the highest hazard in the production. Proper
handling on the reactor should be apply due to operating condition which has the
high temperature and pressure for about 425°C and 350 atm, high concentrations
of HCl and Benzene is flammable.
If the chlorine utilized is cell gas, which contains hydrogen and oxygen,
proper precautions should be taken to ensure that an explosive concentration of
hydrogen does not occur in the vapor stream from the chlorinator nor in the
downstream hydrogen chloride recovery system.
Toxicity Level
Different criteria for the toxicity of each raw material used in the process is
listed to evaluate its toxicity using the Health Hazard Rating provided below.
Table 3.9 Health Hazard Rating
HEALTH HAZARD RATING

For minimal hazard and no significant risk to
0
health
For slight hazard or minor reversible injury
1
possible
For moderate hazard temporary or minor injury
2
may occur
For serious hazard major injury likely unless

3
prompt action is taken and medical treatment given
For severe hazard, life-threatening, major of
4 permanent damage may result from single or
repeated exposures
Table 3.10 Toxicity Levels of Raw Material for Chlorobenzene and Caustic
Process
RAW MATERIALS
CRITERIA Sodium Hydrochloric
Benzene Chlorine
Hydroxide Acid
Inhalation in
high levels of
benzene may
Very
develop
Burning pain, Effects may hazardous if
dizziness,
redness, and include ingested, and
rapid or
Severity of blisters on the sneezing, if with skin
irregular
Immediate skin if exposed sore throat or and eye
heartbeat.
Effects to gas. runny nose contact.
Stomachache,
when Slightly
vomiting and
inhaled. hazardous if
even
inhaled
convulsions
if ingested in
high amounts
Contact with
skin can
Skin contact
Skin injuries cause
may produce
like frostbite irritation or
Sensitization burns. Eye
Irritant can occur if it severe burns.
Level contact may
is exposed to Greater
produce
liquid chlorine exposure can
inflammation
cause
scarring
Insufficient
Carcinogenicity Non – Non -
Carcinogenic evidence for its
Level carcinogenic carcinogenic
carcinogenicity
Reproductive Non - Non - Non –
Mutagenic
Toxicity Level mutagenic mutagenic mutagenic
Complications
are more likely
Chronic
to be seen in
irritation to
Harmful on people who
the eyes,
the bone develop severe
nose, and
marrow and health Severe
upper
Severity of can cause a problems such inflammation
respiratory
Chronic Effects decrease in as fluid in the of the lungs
tract may
red blood lungs can occur
result from
cells, leading (pulmonary
repeated
to anemia edema)
exposure to
following the
the vapors
initial
exposure
Table 3.11 Toxicity Levels of Products for Chlorobenzene and Caustic

Process
PRODUCTS
CRITERIA
Phenol Sodium Chloride
Phenol is toxic with a
probable oral lethal dose to
humans of 50-500 mg/kg.
Some individuals may be
hypersensitive with
lethality or serious effects
May cause eye, skin, and
Severity of at very low exposures.
respiratory tract irritation.
Immediate Rapid absorption and
Hygroscopic (absorbs
Effects severe systemic toxicity
moisture from the air)
can occur after any route of
exposure including skin.
Death and severe toxicity
are usually due to effects
on the CNS, heart, blood
vessels, lung, and kidneys.
Serious skin burns.
Sensitization
Numbness. Convulsions. Irritant
Level
Collapse. Unconsciousness.
There is inadequate
evidence in humans for the
Carcinogenicity
carcinogenicity of phenol. Non – carcinogenic
Level
There is inadequate
evidence in experimental
animals for the

carcinogenicity of phenol.
No reports regarding
Reproductive
Reproductive Toxicity Non – mutagenic
Toxicity Level
Level
Skin exposure results in
pain, then numbness,
blanching, severe burns,
and eschar formation.
Continued exposure can
Severity of Ingestion leads to burning
produce coma, dehydration,
Chronic Effects of throat and severe
and internal organ
gastrointestinal
inflammation. Inhalation
can result in pulmonary
irritation and edema
Table 3.12 Toxicity Level Score for Chlorobenzene and Caustic Process
Raw Materials Products
Hydrochloric
Hydroxide
Chlorine
Chloride
Benzene
Sodium
Sodium
Weight
Phenol
Acid
Criteria
Severity of
Immediate 0.13 4 3 2 4 4 1
Effects
Sensitization
0.07 1 3 2 4 4 1
Level
Carcinogenicity
0.33 4 1 0 0 4 0
Level
Reproductive
0.20 4 0 0 0 0 0
Toxicity Level
Severity of
0.27 4 3 4 3 4 2
Chronic Effects
Weighted Score 3.79 1.74 1.48 1.61 3.2 0.74
Average Weighted
2.09
Score
X. Environmental Impact
In the Production of Phenol Crystals Via Chlorobenzene and Caustic
Process the by-product is an aqueous NaCl solution which will further be fed into
an electrolysis cell.
Table 3.13 Environmental Hazard Rating of Raw Materials

Environmental Hazard Rating
0 For minimal hazard and no significant risk to health.
1 For slight hazard or minor reversible injury possible.
2 For moderate hazard, temporary or minor injury may occur.
For serious hazard, major injury likely unless prompt action is
3
taken and medical treatment given.
For severe hazard, life-threatening, major of permanent damage
4
may result from single or repeated exposures.
Table 3.14 Environmental Hazard Level for Chlorobenzene and Caustic

Process
MAJOR RAW MATERIALS PRODUCTS
Hydroxide (10%)
Chlorine Gas
Hydrochloric
Acid (36%)
Chloride
Benzene
Sodium
Weight
Phenol
Sodium
Measure
Aquatic
0.10 3 0 4 1 3 0
Toxicity
Toxicity on
Plants and 0.20 3 1 3 4 3 0
Animals
Toxicity of
Immediate 0.30 2 1 3 2 2 1
Degradation
Long-term
Degradation 0.40 2 1 3 1 2 1
Effects
Weighted Score 2.3 0.9 3.1 1.9 2.3 0.7
Average Weighted Score 1.87

Raw materials used have no serious effects on environment except for
hydrochloric acid but safety precautions must be taken care of during the
reaction. Hydrochloric acid in the atmosphere may be a much bigger driver of
pollution and damage to the environment, effecting water and land ecosystems
alike. The increased acidity in soil disables some organisms from growing. This
has a chain effect on entire ecosystems, as species lose their habitat, and food.

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Technological Institute of the Philippines

PRODUCTION OF PHENOL VIA

CHLOROBENZENE AND CAUSTIC

PRODUCTION OF PHENOL VIA CHLOROBENZENE AND

Phenol is one of the major raw materials in producing Bis-Phenol A which is

involved in this process are Benzene, Chlorine, Sodium Hydroxide and

II. REACTION MECHANISM

Three reactions are present in the process such as:

` C6H6 + Cl2 85oC, FeCl3 C6H5Cl + HCl

C6H5Cl +NaOH (aq) C6H5NaO

C6H5NaO + HCl(aq) C6H5OH + NaCl(aq)

Figure 3.1 Overall Reaction for Chlorobenzene and Caustic Process

III. PROCESS DESCRIPTION

temperature to form Chlorobenzene in the bubble column reactor.

After the liquid-liquid reaction, unconverted benzene is recycled and

monochlorobenzene is withdrawn all excess chlorine is used in neutralizer and

passed to multi-tube reactor where causticization reaction occurs at the

passed to the neutralizer through the effluent heat exchangers.

Phenol is obtained from hydrolysis occurs at the neutralizer where reaction

Upstream from the separator is sent to vacuum distillation column together

phenol to crystallize having a purity of 99.99%. The mother liquor is separated

IV. EQUIPMENT UTILIZED

Table 3.1 Major Equipment for Chlorobenzene and Caustic Process

1 ST-101 Benzene Storage Tank

2 ST-102 Chlorine Gas Storage Tank

3 ST-103 Iron Chloride Storage Tank

4 ST-104 Sodium Hydroxide Storage Tank

5 ST-105 Hydrochloric Acid Storage Tank

6 ST-106 Sodium Chloride Storage Tank

7 ST-107 Diphenyl Oxide Storage Tank

8 ST-201 Phenol Crystals Storage Tank

9 SC-101 Spray Column

10 R-101 Bubble Column Reactor

11 R-102 Multitube Reactor

15 GS-101 Gravity Settler

16 D-101 Vacuum Distillation Column

Benzene is an aromatic hydrocarbon extracted from cracked gasoline, etc.

chemicals. It is also used as a solvent. For consumer products where benzene is

used as a building block or intermediate, the benzene is typically fully reacted in

a closed system, with little to no benzene remaining in the finished consumer

product. Benzene is naturally found in crude oil.

Figure 3.3 Benzene Storage Containers

Benzene is commercially obtained primarily from pyrolysis gasoline coproduced

in the steam cracking of naphtha, gasoil or condensates to make olefins.

Chlorine, along with its important by-product, sodium hydroxide, is

chloride). The largest use is in the manufacture of poly(chloroethene), PVC,

other major polymers produced using chlorine include the polyurethanes.

in swimming pool water.

However, most chlorine is used in the chemical industry in the

manufacture of other products. Sometimes chlorine is in the product molecule

but on other occasions it is used to produce intermediates in the manufacture of

products that do not contain chlorine and the element is recycled.

Figure 3.4 One Ton of Chlorine Container

Most chlorine is produced on the site on which it is going to be

used, however, some chlorine needs to be transported for example, when it is to

ready for transportation.

Sodium hydroxide (caustic soda) is a clear, slippery, and strong basic

chemical that is a co-product from the manufacture of chlorine using a solution

of the readily available raw material, rock salt (sodium chloride).

strong alkali. Another major use of sodium hydroxide is in the manufacture of

with a solution containing a mixture of sodium sulfide and sodium hydroxide.

Another major use of sodium hydroxide is in the manufacture of paper from

Figure 3.5 Container of NaOH Solution

Hydrochloric acid or muriatic acid is a colorless inorganic chemical