Technological Institute of the Philippines

PROCESS
SELECTION

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PROCESS 1
PRODUCTION OF
POLYHEXAMETHYLENE
ADIPAMIDE (NYLON 6,6)
VIA
POLYCONDENSATION
AND STEP GROWTH
POLYMERIZATION

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PROCESS 1

PRODUCTION OF HEXAMETHYLENE ADIPAMIDE (NYLON 6,6) VIA

POLYCONDENSATION AND STEP GROWTH POLYMERIZATION

I. INTRODUCTION

Synthetic polymers are a substantial part of the textile and plastic

industries. One of the most important classes of synthetic polymers are
polyamides, also known as nylon. One of the of most used polyamides is
Polyhexamethylene Adipamide also called Nylon 6,6. With the growing demand
in for light weight vehicles, of which Hexamethylene Adipamide is a major
component, the market for Polyhexamethylene Adipamide is expected to
increase in the coming years. A step-growth polymerization is a stepwise
reaction between bi-functional or multifunctional monomers in which high-
molecular-weight polymers are formed after a large number of steps. Nylon 6,6
is produced by step-growth polymerization. Due to the nature of the
polymerization mechanism, the reaction has to proceed for a long time to
achieve high molecular weight polymers. In a step-growth polymerization, the
molecular weight of the polymer chain builds up slowly and there is only one
reaction mechanism for the formation of polymer. The distinct initiation,
propagation, and termination steps of chain-growth polymerization are
meaningless in step-growth polymerization. A difunctional monomer or equal
molar amounts of two different difunctional monomers are necessary at least to
form a linear high molecular weight polymer. In the process, the polymerization
reaction proceeds by individual reactions of the functional groups on the
monomers. Thus, two monomers react to form a dimer. The dimer may now
react with another dimer to produce a tetramer. This process continues, each
reaction of the functional groups proceeding essentially at the same reaction rate
until over a relatively long period of time, a high molecular weight polymer is
obtained.

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II. REACTION MECHANISM

Phase 1: Oxidation of Cyclohexane

Reaction 1: C 6 H 12 +O 2 → C6 H 11 OOH

Reaction 2: 3C 6 H 11 OOH →2 C 6 H 11 OH +C 6 H 10 O+ H 2 O+O 2

Phase 2: Oxidation of KA Oil (Cyclohexanone/Cyclohexanol Mixture)

Reaction 1: 4 C6 H 11 OH +6 HN O3 → 4 C 6 H 10 O4 +3 H 2 O+3 N 2 O

Reaction 2: 3 C6 H 11 OH +2 HNO3 →C 6 H 10 O 4 +2 H 2 O+ N 2 O

Phase 3: Synthesis of Hexamethylene Adipamide (Nylon 6,6)

Reaction 1:C 6 H 16 N 2+ C6 H 10 O4 → C6 H 26 N 2 O4

Reaction 2:C 6 H 16 N 2+ C6 H 10 O 4 → C6 H 22 N 2 O 2+2 H 2 O

III. PROCESS DESCRIPTION

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The overall process involves 3 phases in order to produce

Polyhexamethylene Adipamide (Nylon 6,6).

Oxidation of Cyclohexane:

The cyclohexane from a storage tank will enter in heat exchanger to prepare
the cyclohexane for the oxidation process. The oxidation takes place in four
series agitated oxidation reactors. Air is blown from the bottom of each
oxidation reactors while the agitator spins in a specific rpm. The oxidation of
cyclohexane takes place with a cobalt naphthenate catalyst. The reacted mixture
from the reactors will proceed to the centrifuge to separate unreacted
cyclohexane and recycled back to oxidation reactors. The mixture from the
centrifuge will proceed to another oxidation process to oxidize KA Oil which is
the mixture of cyclohexanone and cyclohexane using nitric acid to produce
adipic acid.

Oxidation of KA Oil:

The mixture from centrifugation process is fed to KA Oil oxidation reactor

with nitric acid, the reactor is operated at 90 ℃. After the oxidation process,
liquid mixture will be cooled using a heat exchanger before going to a
crystallizer where the adipic acid crystals is being produced. Adipic acid crystals
will be concentrated by evaporating excess water and nitric acid using an
evaporator.

Nitrous oxide byproduct from KA Oil oxidation reactor will proceed to

NOx bleacher to convert it to nitrogen dioxide using air. The resulting mixture
will go to NOx Absorber to convert nitrogen dioxide into nitrogen oxide and will
be withdrawn together with inert gases, nitric acid and water byproduct from this
equipment will be recycled to KA Oil oxidation reactor. Concentrated adipic
acid crystals from evaporator will be fed into a conveyor to use it on
polycondensation and polymerization process.

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Polycondensation and Step growth polymerization:

Hexamethylene Diamine powder is fed to a mixer and mixed with heated

deionized water in an equimolar ratio. After the stream leaves the mixer, it is
sent to a continuous stirred tank reactor (CSTR) where the Hexamethylene
Diamine is reacted with solid Adipic Acid from the evaporator to form Nylon 66
salt. The salt solution is then pumped into an evaporator to remove some of the
water. After the solution leaves the evaporator, it is pumped into a jacketed
continuous stirred tank reactor where the polymerization reaction occurs,
Polyhexamethylene Adipamide or Nylon 6, 6 formed. The water formed during
the reaction is sent to a condenser to condense it. After the Nylon 6,6 leaves the
reactor, it is pumped through a cooler to aid with extrusion and is then sent
through extruder which produces Polyhexamethylene Adipamide (Nylon 6,6)
fibers.

IV. EQUIPMENT UTILIZED

Table 6.1 List of Major Equipment for Production of Polyhexamethylene

Adipamide

NO. EQUIPMENT CODE EQUIPMENT NAME

1 T-101 Cyclohexane Storage Tank
2 P-100 Pump
3 HEX-101 Heat Exchanger 1
4 OR-101 Oxidation Reactor 1
5 OR-102 Oxidation Reactor 2
6 OR-103 Oxidation Reactor 3
7 OR-104 Oxidation Reactor 4

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8 AC-001 Air Compressor 1

9 HEX-102 Heat Exchanger 2
10 HEX-103 Heat Exchanger 3
11 CF-101 Centrifuge
12 KR-101 KA Oil Oxidation Reactor
13 T-102 Nitric Acid Storage Tank
14 AC-002 Air Compressor 2
15 NX-101 NOx Bleacher
16 NA-101 NOx Absorber
17 T-104 Water Storage Tank
18 HEX-104 Heat Exchanger 4
19 AAC-101 Adipic Acid Crystallizer
20 EV-101 Evaporator
21 CD-001 Condenser 1
22 X-102 Adipic Acid Conveyor
23 X-103 HMDA Conveyor
24 X-104 Solid Adipic Acid Hopper
25 X-105 Solid HMDA Hopper
26 T-103 Water Storage Tank 2
27 HEX-105 Heat Exchanger 5
28 MX-101 Mixer
29 P-101 Pump 1
30 R-101 Nylon Salt Reactor
31 P-102 Pump 2
32 FE-101 Falling Film Evaporator
33 P-103 Pump 3
34 R-102 Polymerization Reactor
35 P-104 Pump 4

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36 C-101 Cooler
37 X-106 Yarn Extruder

PROCESS FLOW DIAGRAM

Type equation here .

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Figure 6.1: Production Of Hexamethylene Adipamide (Nylon 6,6) via Polycondensation

And Step Growth Polymerization

V. RAW MATERIALS

Hexamethylene Diamine

Hexamethylene Diamine, also known as 1, 6-Hexanediamine, is an

organic compound that can appear as a clear colorless liquid or a colorless
crystalline solid. It derives from a hydride of a hexane. Hexamethylene Diamine
is widely used for the production of polymers, it can be used as a reagent used to
modify acrylonitrile copolymers and to polycondense with compounds such as
calcein.

Figure 6.2: Hexamethylene Diamine (Solid)

Cyclohexane

Cyclohexane, an alicyclic hydrocarbon comprising a ring of

six carbon atoms, is a colorless flammable liquid and volatile organic compound
with a petroleum-like odor. It can be used as a raw material for the production of

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nylon, raw material for the production of adipic acid and caprolactam as a
solvent, a paint remover, and to make another chemical. It is commercially
produced via hydrogenation of benzene.

Figure 6.3: Cyclohexane

Nitric Acid

Nitric Acid, also known as aqua fortis and spirit of niter, is a nitrogen
oxoacid having a formula of HNO . It is a colorless (though older samples tend
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to appear as yellow due to decomposition into oxides of nitrogen and water)

liquid that is mainly used in the manufacture of inorganic and organic nitrates
and nitro compounds fertilizers, explosives, dye intermediates, and many
different organic chemicals. It is a highly corrosive acidic substance and a strong
oxidizing agent which is a substance that readily accepts electrons from another
substance.

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Figure 6.4: Nitric Acid

VI. SUSTAINABILITY:

Availability of Raw Materials:

The raw materials for this process are already available in the Philippines
and it consists of Hexamethylene Adipamide, Nitrogen Gas, Oxygen Gas,
Cyclohexane and Nitric Acid. The availability of the raw materials will greatly
affect the process for continuous procedure.

Table 6.2: Supplier of Raw Materials for Polycondensation and Step-growth Polymerization

RAW MATERIAL SUPPLIER

1 Hexamethylene EURO CHEMICALS INC.

Lot 2 Arty II, Corner Road 1, Brgy Mindanao
Adipamide Avenue, Quezon City, Metro Manila
Website: [Link]
Landline: (02) 8930 4715
Distance from Plant: 90.8 (94 min)

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2 Cyclohexane J.E MANALO & CO., INC

1188 Bernal Street, Pasig, 1609 Metro Manila
Website: [Link]/
Landline: (02) 641-2796 – 98
Distance from Plant: 136 km (164 min)
3 Nitric Acid TNC CHEMICALS PHILIPPINES, INC.
Petron Mega Plaza, Makati, 1200 Metro
Manila
Website: [Link]//
Landline:  (02) 8403 7725
Distance from Plant: 138 km (170 min)

DEMAND AND SUPPLY OF RAW MATERIALS

Hexamethylene Diamine

The Hexamethylenediamine Market was valued at 5.98 Billion USD in

2018 and is projected to register at 5.65% during the forecast period. The Global
Hexamethylenediamine Market has been analyzed for five major regions,
namely, North America, Asia-Pacific, Europe, Latin America, and the Middle
East & Africa. The market in Asia-Pacific dominates the global
hexamethylenediamine market and is projected to register the highest CAGR
during the forecast period owing to the rapid industrialization in the region. The
increased use of hexamethylenediamine as a precursor to producing nylon 6, 6 in
end-use industries, such as automotive and textile, is expected to drive the
regional market demand. China is the largest consumer in the region on account
of rising exports of nylon from the country. For instance, in 2018, the total nylon
exports from China were valued at USD 137.70 million. Thus, making it among
the top three global nylon exporters. Furthermore, India and other South-East
Asian countries are propelling the regional market growth on account of the
increasing use of the product in the water treatment industry. These factors

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create numerous opportunities for the players operating in the

hexamethylenediamine market in the region.

The market in North America accounted for a substantial market share in

2018. The growing demand for hexamethylenediamine as a raw material in the
paints and coating industry and the increasing constructional activities in the
region are driving the growth of the regional market. In addition, the rising
advancements in the US, coupled with emerging multifunctional applications
such as in 3D printing and functional coatings, are further driving the regional
market growth. The market in Europe is expected to showcase significant
growth during the forecast period. This can be attributed to the increasing use of
hexamethylenediamine to manufacture automotive components and produce
lubricants. The markets in Latin America and the Middle East & Africa are
expected to show healthy growth during the forecast period owing to the
growing paints and coatings industry. The increasing use of HMDA in the
petrochemical industry is further fueling regional market growth.

Figure 6.5: World Consumption of Hexamethylene Diamine

Source: [Link]

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Cyclohexane

The global cyclohexane market size was estimated at 9,192.4 kilo tons in
2016. Increasing consumption of automotive and textile applications are
expected to be a key factor driving growth.  Cyclohexane is an intermediate
product, which is used for the production of adipic acid and caprolactam.
Increasing applications of cyclohexane in various industries along with the
growing demand for nylon products in automotive and engineered plastics are
major drivers of the global cyclohexane market growth. The product is also
getting traction in food and beverage packaging, textile, and electrical &
electronics which initiated several legislative actions and regulations regarding
its safe usage. The cyclohexane is used to produce adipic acid and caprolactam
which are further utilized to manufacture many ends use products such as nylon
6, nylon 66, and others. Nylon being an end-use product can be used to make a
thread which can be further transformed to textile and clothing. Caprolactam is
the primary feedstock for the manufacturing of nylon 6, although adipic acid is
majorly used to produce nylon 66. In the first half of 2013, as the global crude
oil prices showed signs of decreasing caprolactam manufacturers were making
substantial revenue as their operating to gateway price ratio were balanced.
Government initiatives coupled with increased awareness about nylon products
surged the demand for cyclohexane end-use. The low production cost, relaxed
government regulations, and growth in nylon consumption further boosted the
demand globally. Asia Pacific was leading the cyclohexane consumer;
accounted for over 38.3% of the total revenue in 2016. Emerging economies in
the region including India and China, are developing economies; undergoing
significant economic changes. Growing population and increasing living
standards spurred the cyclohexane demand in the area. China is the largest
producer and consumer of cyclohexane globally. China’s rapid urbanization,
supported by strong economic growth resulted in an active cyclohexane market.
Due to growing awareness and increasing disposable income, the country is

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witnessing a shift from traditional to bio-based cyclohexane production. Europe

accounts for over 23.7% of the total global volume in 2016. Growing
consumption mainly in the U.S. and China coupled with easy regulations
regarding quality are expected to remain key driving factors for the industry.
Also, abundant raw material availability is also expected to drive the
cyclohexane demand over the forecast period.

Figure 6.6: Cyclohexane Market Volume

Source: [Link]

Nitric Acid

The global nitric acid market size was valued at 24.0 billion USD in
2019 and is anticipated to register a CAGR of 3.3% from 2020 to 2027.
Increasing demand for adipic acid to formulate nylon resins and fibers for
automotive interior manufacturing is identified as a key market driver. It is
widely used as a precursor for the production of nylon 6,6, which is extensively
used in the automotive sector globally. One of the key applications of nitric acid
is the formulation of adipic acid. Nylon, which is formulated from adipic acid, is
extensively used by automobile manufacturers.

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The North America market is projected to witness significant growth over the
forecast period owing to the presence of a large number of multinational
chemical manufacturers in the U.S. The nitric acid market is expected to further
reflect high growth due to the rapid development of industries such as
construction, automobile, agriculture, and furniture. These industries require
high-quality nitric acid to formulate fertilizers and nylon. Furthermore, there has
been an increasing demand for ammonium nitrate from the mining industry to
formulate explosives, which, in turn, drives the overall market growth. Germany
houses some of the largest automobile manufacturers in the world. Key
companies include Volkswagen, BMW, Daimler AG, Adam Opel, and Ford-
Werke GmbH. This resulted in high demand for nylon products for automobile
interiors and component manufacturing in the country. However, as of 2020, the
industry reflected an all-time low production of around 4.7 million vehicles in
2019. This was mainly due to the rising trade tension between China and the
U.S., which impacted the foreign markets and thereby resulted in low demand.
Central and Eastern Europe are among the largest producers of nitric acid,
thereby driving the regional market. Furthermore, the growing chemical market
in Poland and Russia is expected to drive the European market. Russia is a
leading exporter of arms and hence witnesses high demand for ammonium
nitrate, thus positively impacting the market growth. Robust manufacturing base
for fertilizers in Russia on account of the availability of raw materials such as
ammonia is also anticipated to have a positive impact on the market. Moreover,
in 2014, the Indian government declared Draft National Chemical Policy,
intended to increase the share of the chemical sector in the country’s GDP from
3% in 2014 to 6% by 2020. This regulatory move is expected to promote the
production of chemicals such as nitrobenzene, TDI, and adipic acid, which is
expected to drive the Asia Pacific market over the forecast period.

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In addition, the growth of the fertilizer market in India on account of

regulatory support aimed at increasing the production capacity of urea and other
agrochemicals is expected to drive the demand for nitric acid.

Figure 6.7: World Consumption of Nitric Acid

Source: [Link]

VII. PLANT ECONOMY

The total capital investment and annual cost production for

Polycondensation and Step Growth Polymerization process is calculated in this
section.

EQUIPMENT COST

The method used to calculate the estimated capital cost for the
Production of Polyhexamethylene Adipamide via Polycondensation and Step
Growth Polymerization is Lang method. The Lang factors were taken from the
Perry’s Chemical Engineering Handbook 8th Edition and the method used
depends on the type of processing equipment.

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Table 6.3: Lang factors (Green and Perry 2008)

Type of Plant Lang Factors

Fixed Capital Total Capital
Investment Investment
Solid Processing 4 4.7
Solid Fluid Processing 4.3 5
Fluid Processing 5 6

Formula for the computation of Fixed Capital Cost was taken from Chemical
Engineering Design Volume 6 by Coulson and Richardson.
C f =f L Ce

Where, C f = fixed capital cost

f L = “Lang Factor” which depends on the process type

Ce = total delivered cost of all the major equipment items

Assuming the equipment delivery charge is 5% of the purchased equipment cost.

Table 6.4: Cost of Equipment for Polycondensation and Step-Growth Polymerization

EQUIPMENT QTTY. EQUIPMENT DELIVERED PEC=DEC x

COST (PHP) EQUIPMENT FACTOR
COST
Storage Tank 4 ₱1,655,460 ₱1,738,233.00 ₱8,691,165.00
Air 2 ₱632,970 ₱664,618.50 ₱3,323,092.50
Compressor
Oxidation 4 ₱4,869,000 ₱5,112,450.00 ₱25,562,250
Reactor
Centrifuge 1 ₱73,0350 ₱766,867.50 ₱3,834,337.5
Cooler 1 ₱486,900 ₱511,245.00 ₱2,556,225
Heat 5 ₱3,651,750 ₱3,834,337.50 ₱19,171,687.5
Exchanger
Absorber 1 ₱2,434,500 ₱2,556,225.00 ₱12,781,125
Crystallizer 1 ₱584,280 ₱613,494.00 ₱3,067,470
Falling Film 1 ₱925,110 ₱971,365.50 ₱4,856,827.5
Evap.

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Hopper 2 ₱779,040 ₱817,992.00 ₱4,089,960

Conveyor 2 ₱97,380 ₱102,249.00 ₱511,245.00
Pump 5 ₱292,140 ₱306,747.00 ₱1,533,735
Evaporator 1 ₱1,460,700 ₱1,533,735.00 ₱7,668,675
Condenser 1 ₱925,110 ₱971,365.50 ₱4,856,827.5
Extruder 1 ₱550,197 ₱577,706.85 ₱2,888,534.25
Poly reactor 1 ₱730,350 ₱766,867.50 ₱3,834,337.5
KA Oxidation 1 ₱973,800 ₱1,022,490.00 ₱5,112,450
Reactor
Nylon Salt 1 ₱1,241,595 ₱1,303,674.75 ₱6,518,373.75
Reactor
Bleacher 1 ₱486,900.00 ₱511,245.00 ₱2,556,225
Mixer 1 ₱97,380.00 ₱102,249.00 ₱511,245.00
Purchasing 37 ₱23,604,912 ₱24,785,157.6 ₱123,925,788
Equipment
Cost:

PROJECT COST

The project fixed capital cost necessary for the production of poly-
hexamethylene adipamide via polycondensation and step-growth polymerization
was calculated using the typical factors for estimation of project’s capital cost
from Chemical Engineering Design.

Table 6.5: Typical factors for Estimation of Project’s Fixed Capital Cost

Process Type
Item
Fluid Fluids-Solids Solids
1. Major Equipment,
PCE PCE PCE
Total Purchase Cost
f1 Equipment
0.4 0.45 0.5
Erection
f2 Piping 0.7 0.45 0.2
f3 Instrumentation 0.2 0.15 0.1
f4 Electrical 0.1 0.1 0.1
f5 Buildings, process 0.15 0.1 0.05
*f6 Utilities 0.5 0.45 0.25
*f7 Storages 0.15 0.2 0.25

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*f8 Site Development 0.05 0.05 0.05

*f9 Ancillary
0.15 0.2 0.3
Building
2. Total physical
Plant Cost (PPC)
PPC = PCE (1+f1+ 3.4 3.15 2.8
……+ f9)
PCEx
f10 Design and
0.3 0.25 0.2
Engineering
f11 Contractor’s Fee 0.05 0.05 0.05
f12 Contingency 0.1 0.1 0.1
3. Fixed Capital =
PPC (1+ f10 +f11 + f12) 1.45 1.4 1.35
PPC
Adapted from Coulson and Richardson, Chemical Engineering Design, Volume 6

Physical Plant Cost (PPC)

Physical Plant Cost = (PCE) (1+f1+……+ f9)

PPC = ₱123,925,788 (3.15)

PPC = ₱ 390,366,232.20

Fixed Capital Cost (FCC)

Fixed Capital Cost = (PPC) (1.4)

FCC = ₱ 390,366,232.20 (1.4)

FCC = ₱ 546,512,725.08

Working Capital Cost (WCC)

Working Capital Cost = (FCC) (0.05)

WCC = ₱ 546,512,725.08 (0.05)

WCC = ₱ 27,325,636.25

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Total Capital Investment

Total Capital Investment = FCC + WCC

TCI = ₱ 546,512,725.08 + ₱ 27,325,636.25

TCI = ₱ 573,838,361.33

FIXED COST, VARIABLE COST, AND OTHER COST

The operating cost that is used for the production of poly-hexamethylene

adipamide via polycondensation and step-growth polymerization was calculated
using costing and project evaluation from Chemical Engineering Design, volume
6.

Figure 6.8: Costing and Project Evaluation

Source: Peter and Timmerhaus

FIXED COSTS

Maintenance Cost (MC)

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Maintenance Cost: FCC (0.10)

MC: ₱ 546,512,725.08 (0.10)

MC: ₱ 54,651,272.51

OPERATING LABOR COST

For plant capacity of 200 MT per day and for an average condition, the
estimated operating labor equipment is 50 employee-hours/day/processing step
day considering the three processing steps and 300 days operating time per year.
The estimated operating labor requirement was estimated using Figure 6.1.2.

Figure 6.9: Operating Labor Requirements

Table 6.6: Summary of Current Regional Daily Minimum Wages Rates

Region SECTOR

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IV-A Non-agriculture Agriculture

Plantation Non-Plantation
400 372 372
Source: Department of Labor and Employment 2020

Operating Labor Cost = Operating Labor x Operating Time x Wage x Processing

Steps

OLC:

55 employee−hours 300 working days P 400

x x
day −processing year employee−8 hr

x 3 processing x 1 year operation

OLC: ₱ 2,475,000.00

Laboratory Cost (LC)

Laboratory cost: (OLC) (0.23)

Laboratory Cost: ₱ 2,475,000.00 (0.23)

LC: ₱ 569,250.00

Supervision Cost (SC)

Supervision Cost: (OLC) (0.20)

Supervision Cost: ₱ 2,475,000.00 (0.20)

SC: ₱ 495,000.00

Plant Overheads (PO)

Plant Overheads: (OLC) (0.50)

Plant overheads: ₱ 2,475,000.00 (0.50)

PO: ₱ 1,237,500.00

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Capital Charges (CC)

Capital Charges = (FCC) (0.10)

Capital Charges = ₱ 546,512,725.08 (0.10)

CC: ₱ 54,651,272.51

Local Taxes (LT)

Local Taxes = (FCC) (0.02)

Local Taxes = ₱ 546,512,725.08 (0.02)

LT = ₱ 10,930,254.50

Insurance (I)

Insurance = (FCC) (0.01)

Insurance = ₱ 546,512,725.08 (0.01)

I = ₱ 5,465,127.25

License Fee / Royalty Fee (LF/RF)

License Fee / Royalty Fee = (FCC) (0.01)

License Fee / Royalty Fee = ₱ 546,512,725.08 (0.01)

(LF/RF) = ₱ 5,465,127.25

Table 6.7: Summary of Fixed Cost for Polycondensation and Step-Growth

Polymerization Process

FIXED COSTS  
Maintenance Cost ₱ 54,651,272.51

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Operating Labor Cost ₱ 2,475,000.00

Laboratory Cost ₱ 569,250.00
Supervision Cost ₱ 495,000.00
Plant Overheads ₱ 1,237,500.00
Capital Charges ₱ 54,651,272.51
Local Taxes ₱ 10,930,254.50
Insurance ₱ 5,465,127.25
License Fee/Royalty Fees ₱ 5,465,127.25
TOTAL FIXED COST ₱ 135,939,804.02

VARIABLE COSTS

Miscellaneous Operating Materials (MOM)

Miscellaneous Operating Materials = (Maintenance Cost) (0.10)

Miscellaneous Operating Materials = ₱ 54,651,272.51 (0.10)

MOM: ₱ 5,465,127.25

RAW MATERIAL COST:

Table 6.8: Raw Material for Polycondensation and Step-Growth Polymerization

Process

Raw Material Cost (PHP/ 10 MT)

HMDA ₱ 1,271,188.00
Cyclohexane ₱ 811,426.70
Nitric Acid ₱ 316,000
TOTAL: ₱ 2,398,614.70

Table 6.9: Summary of Variable Cost for Polycondensation and Step-Growth

Polymerization Process

VARIABLE COSTS
 
Miscellaneous Operating Materials ₱ 5,465,127.25
Raw Materials Cost ₱ 2,398,614.70

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TOTAL VARIABLE COST ₱ 7,863,741.95

DIRECT PRODUCTION COST (DPC)

Direct Production Cost = VC + TFC

Direct Production Cost = ₱ 7,863,741.95 + ₱ 135,939,804.02

DPC = ₱ 143,803,545.97

OTHER COSTS

Sales Expense (SE)

Sales Expense = Direct Production Cost (0.20)

Sales Expense = ₱ 143,803,545.97 (0.20)

SE = ₱ 28,760,709.19

General Overheads (GO)

General Overheads = (DPC) (0.25)

General Overheads = ₱ 143,803,545.97 (0.25)

GO: ₱ 35,950,886.49

Research and Development (R&D)

Research and Development = (DPC) (0.28)

Research and Development = ₱ 143,803,545.97 (0.28)

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R&D = ₱ 40,264,992.87

Table 6.10: Summary of Other Costs for Polycondensation and Step-Growth

Polymerization Process

OTHER COSTS
 
SE ₱ 28,760,709.19
GO ₱ 35,950,886.49
R&D ₱ 40,264,992.87
TOTAL OTHER COST ₱ 104,976,588.56

ANNUAL PRODUCTION COST (APC)

Annual Production Cost = DPC + OC

Annual Production Cost = ₱ ₱ 143,803,545.97 + ₱ 104,976,588.56

APC = ₱ 248,780,134.53

PRODUCTION COST:

Annual Production Cost

Production Cost = Plant capacity days
( day )
(300 working
year
)

₱ 248,780,134.53
Production Cost = 200 MT days
( )(300 working )
day year

Production Cost = ₱ 4,146.34

VIII. MANUFACTURABILITY

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PURITY

The Polyhexamethylene Adipamide obtain from Polycondensation and Step-

Growth Polymerization Process has a purity of 99.9%.

YIELD

The Polyhexamethylene Adipamide obtain from the Multi-stage Distillation

Column Reactor Process has a yield 86.58%.

PROCESS USAGE

The Production of Polyhexamethylene Adipamide via Polycondensation

and Step-Growth Polymerization Process is being used by Allied Chemical,
Celanese Corporation, Du Pont Orange, Du Pont Victoria and Monsanto.

IX. SAFETY

Table 6.11: Parameters for Polycondensation and Step-Growth Polymerization Process

PARAMETERS RANGE

Temperature 400 ºC

Pressure 1 atm

TOXILOGICAL RATING

The toxicity of raw materials is examined based on the health hazards

level that can harm people. The health hazards of the raw material are based

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from the Material Safety Data Sheet and the table below was used to evaluate
the toxicity level.

Table 6.12: Health Hazard rating for Polycondensation and Step-Growth

Polymerization Process

HEALTH 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

3 For serious hazard, major injury likely unless prompt action is taken,
medical treatment given

4 For severe hazard, life-threatening, major of permanent damage may

result from single or repeated exposures

Table 6.13: Toxicity Level Scores of Raw Materials and Products for Polycondensation
and Step-Growth Polymerization Process

   
Criteria Wt. Major Raw Materials Product

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C 6 H 12 Nylon
HMDA Nitric Acid
6,6
Severity of
Immediate 0.1 4 2 2 0
Effects
Sensitization
Level
0.1 4 2 3 1
Carcinogenity
0.3 0 0 0 1
Level
Reproduce
Toxicity 0.25 3 0 0 0
Level
Severity of
Chronic 0.25 4 4 2 1
Effects
Weighted  
Score
2.55 1.4 1 0.65
Average
Weighted 1.316666667
Score

Table 6.14: Basis of Toxicity Level Scores for Raw Materials for Polycondensation and
Step-Growth Polymerization Process

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Criteria Raw Materials

HMDA Cyclohexane Nitric Acid

Severity of May cause eye Prolonged contact may Prolonged contact

Immediate irritation, skin damage cause eye irritation and may cause eye
Effects and difficulty in skin burn irritation and skin
breathing burn

Sensitization Irritant Irritant Irritant

Level

Carcinogenicity Not listed as Not listed as carcinogen Not listed as

Level carcinogen carcinogen

Reproduce Mutagenic Non- Mutagenic Non- Mutagenic

Toxicity Level

Severity of Prolonged eye and skin Prolonged contact may Prolonged contact
Chronic Effects contact may cause cause damage to liver and may cause
severe eye and skin kidneys. abdominal pain.
damage and difficulty
in breathing

Table 6.15: Basis of Toxicity Level Scores for Polycondensation and Step-Growth
Polymerization Process

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Criteria Product

Nylon 6,6

Severity of Immediate May not cause skin, eye and lung

Effects damage

Sensitization Level Irritant

Carcinogenicity Level Carcinogenic in some aspects

Reproduce Toxicity Non-mutagenic

Level

Severity of Chronic May cause severe itchiness as

Effects textile.

X. ENVIRONMENTAL IMPACT

The basis for the environmental hazard for the Production of

Polyhexamethylene Adipamide via Polycondensation and Step-Growth
Polymerization Process is the raw materials and product. The environmental
hazard data is based on the harmful effects of the materials to the environment
and the table below was used to evaluate the toxicity level.

Table 6.16: Environmental Hazard Rating

ENVIRONMENTAL HAZARD RATING

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0 For minimal hazard and no significant risk to the environment

1 For slight hazard or minor reversible damage possible

2 For moderate hazard, temporary or minor damage may occur

3 For serious hazard, major damage to environment unless prompt

action is taken

4 For severe hazard, permanent damage may result

Table 6.17: Environmental Hazard Level Scores of Raw Materials and Products

Major Raw Materials Product

Criteria Weight
C 6 H 12 Nylon
HMDA Nitric Acid
6,6

Aquatic
0.2 2 0 2 0
Toxicity
Toxicity on
Plants and 0.25 2 1 2 0
Animals
Toxicity of
Immediate 0.2 0 0 0 0
Degradation
Long-term
Degradation 0.35 3 2 2 1
Effect
 
Weighted Score 2.2 0.95 1.6 0.35

Average  
1.32
Weighted Score

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Table 6.18: Basis of Environmental Hazard Level Scores for Raw Materials

Criteria Raw Materials

HMDA Nitric Acid

Cyclohexane

Aquatic Dangerous to Dangerous to

Toxicity Aquatic Life No known toxic Aquatic Life
effects
Toxicity on Dangerous for plants Dangerous for
Plants and and animals Dangerous for plants plants and
Animals and animals animals

Toxicity of No known toxic No known toxic

Immediate effects No known toxic effects
Degradatio effects
n
Long-term No known toxic No known toxic
Degradatio effects No known toxic effects
n Effect effects

Table 6.19: Basis of Environmental Hazard Level Scores for Products

Criteria Product

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Nylon 6,6

Aquatic Toxicity No known toxic effects

Toxicity on Plants and Animals No known toxic effects

Toxicity of Immediate Degradation No known toxic effects

Long-term Degradation Effect No known toxic effects

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PROCESS 2
PRODUCTION OF
POLYHEXAMETHYLENE
ADIPAMIDE FROM
ADIPONITRILE VIA
MULTI-STAGE
DISTILLATION COLUMN
REACTOR

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Production of Poly-Hexamethylene Adipamide from Adiponitrile via Multi-

stage Distillation Column Reactor

I. INTRODUCTION:

Poly-Hexamethylene Adipamide also known as Nylon 6,6, is one of the

most versatile engineering thermoplastics. It is popular in every major market
using thermoplastic materials. Because of its excellent balance of strength,
ductility and heat resistance, Nylon 6,6 is an outstanding candidate for metal
replacement applications. Nylon 6,6 is very easy to process with a very wide
process window. This allows it to be used for everything from complex, thin-
walled components to large thick-walled housings.

This invention is a method of continuous process for the manufacture of

Nylon 6,6 from adiponitrile providing a vertical countercurrent multistage
reactor having a top and a bottom, and having upper stages and lower Stages
wherein the introducing of the adiponitrile containing reactant stream and the
introducing of the hexamethylenediamine containing stream are adapted to
provide a nylon 6,6 containing product in which the nylon 6,6 is characterized
by balanced amine and acid ends. The adiponitrile is hydrolyzed by reacting
with dissolved water which is supplied and replenished by steam flowing
counter-currently to the direction of flow of the adiponitrile and subsequent
reaction products, and the adiponitrile hydrolysis product is polymerized with
hexamethylenediamine under the operating conditions of the column to form a
nylon 6.6 polyamide.

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II. REACTION MECHANISM:

I. C 6 H 10 O 4 +2 NH 3 →C 6 H 8 N 2 +4 H 2 O
II. C 6 H 8 N 2 +4 H 2 O+C6 H 16 N 2 →C 12 H 22 N 2 O2 +2 NH 3 +2 H 2 O

III. PROCESS DESCRIPTION:

Evaporator:

Adipic acid is fed to the evaporator, usually at a temperature just above

its melting point. In this system ammonia at about 20°C is passed by to the
heater where its temperature is raised to about 430° C to 450° C. Molten adipic
acid at about 160° C is passed to the evaporator where it is usually spread out in
a thin film, either on the walls of the evaporator or on a packing material, such
as Raschig rings contained therein. The high temperature ammonia conducted to
the evaporator serves to vaporize and or entrain the adipic acid. The evaporator
is provided at its bottom with a reservoir suitable for containing a liquid and the
processing conditions are so arranged that about 1% of the adipic acid fed to the
evaporator is not evaporated, but rather carries any tars produced in the reaction
to the bottom of the evaporator whence they may be conveniently withdrawn.

Reactor 1:
The ammonia vapors having adipic materials dissolved or entrained is
conducted to a tubular reactor where it is passed, usually downwardly, through
narrow tubes filled with a dehydration catalyst. This catalyst may
advantageously be phosphoric acid distended on a silica gel support. The vapor
mixture is introduced to the reactor at a temperature greater than 300° C,
preferably about 340°C-360° C, and also is removed from the reactor at a
temperature greater than about 300° C and usually at slightly greater than
atmospheric pressure. 50 moles of NH3 are provided for each mole of adipic
acid and this excess ammonia sweeps the formed adiponitrile vapor from the

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reactor at a temperature of about 310°C through the cooler and to the to the
fractionation column.
Fractionation Column:
Ammonia vapors are removed from the column for recycle to the
evaporator. Make-up ammonia is added to the system to the pump. Ammonia,
heated to only about 360°C to 380° C is fed to a wiped film evaporator which is
externally heated to maintain a temperature of about 350°C -380°C. The
residence time of the adipic material in the reactor often is about 4 seconds.

Cooler:

After leaving the reactor the mixture, comprising primarily ammonia,

adiponitrile and water is cooled to about 20° C. The adiponitrile, which usually
amounts to about 80.4% of theory yield, is removed, along with water. Cooler
may chill the mixture to about room temperature and separated into its
components. The ammonia is recycled to the evaporation step.

Multistage Distillation Column Reactor:

The internal configuration of a multistage reactor is divided into discrete

stages using perforated barriers between the stages. The barriers can be plates
having small perforations which allow the vapor to flow upward from stage to
stage, and a larger downcomer tube which leads from each stage into and below
the surface of the reaction mixture in the stage below, allowing the liquid to flow
downward from stage to stage. The number of stages is chosen to achieve a high
rate, per unit of liquid volume, of mass transfer and chemical reaction. Five to
fifteen stages are typical. The adiponitrile is fed continuously near the top of the
multistage column reactor and steam is fed continuously to one or more stages at
or near the bottom of the reactor. The hexamethylenediamine feed is fed
continuously to one or more stages of the column reactor that are located below
the stage at which adiponitrile is introduced. Steam and ammonia vapor are

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removed at the top of the column as vapor stream. Nylon 6,6 polyamide product
is continuously removed from the bottom stage. The column preferably includes
means to separate and return to the column any adiponitrile and/or
hexamethylene diamine which leaves the top part of the column as a vapor or as
an entrained liquid. The top temperature is maintained at a temperature that is
high enough to achieve a good rate of hydrolysis of the adiponitrile, while
avoiding excessive volatilization of adiponitrile and/or hexamethylenediamine.
The potential for forming secondary amines exists throughout the column;
therefore, it is important that the average temperature of the stages not exceed a
value above which the formation of secondary amines becomes detrimental to
the product.
Because the hydrolysis reaction is exothermic, the column is optionally
equipped with means for water injection at all or selected stages for temperature
control. The top stage is preferably maintained between about 190° C and
250°C, and the bottom stage is preferably operated between about 260°C. The
column is operated at elevated pressure, preferably above 50 psig (0.34MPa),
more preferably 100 to 300 psig (0.69 to 2.07 MPa) with catalyst and 400 to 800
psig (2.76 to 5.52 MPa) without catalyst to obtain substantially complete
hydrolysis of the nitrile ends in the adiponitrile, which is required to obtain good
quality polymer. The ammonia is removed from the reactor in vapor Stream. It is
important to minimize the concentration of ammonia in the lower part of the
column for two reasons: (1) ammonia reacts with and breaks amide linkages,
hence limiting the growth of polymer molecular weight, and (2) ammonia in the
vapor reduces the partial pressure of Steam in the vapor and hence the
concentration of water dissolved in the liquid, which reduces the rate of nitrile
hydrolysis.

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Mixing:

At the bottom of the column, where the viscosity is highest, a mixer is

preferably used in one or more of the bottom most stages in the reactor.
Preferably, to minimize liquid by-pass between the stages, mixing in each stage
is induced by either proper arrangement of coils, to assist gas induced mixing, or
by mechanical agitation in lower Stages, where gas mixing is not sufficient due
to high viscosities. Liquid by-pass reduces the desired reaction efficiency
resulting in either a requirement for a larger size reactor to achieve the same
conversion at a given flow rate and increased ratio of side reactions to preferred
reaction, resulting in quality problems.
Axial mixing between the stages in the column reactor as a result of
liquid backflow through the downcomers will reduce the overall nitrile
conversion efficiency in the column reactor. Preferably the reactor Stages are
configured as flooded trays to facilitate an agitator shaft to pass through the
downcomers to avoid sealing a rotating shaft against liquid. Typically,
mechanical mixing is required at the bottom two or three stages of the reactor to
minimize liquid by-pass. The nylon 6,6 polyamide product removed from the
bottom of the column. The product contains a content of dissolved water more or
less proportional to the pressure of the column reactor. The mixture pass through
a pipe to bring about most of the reduction in pressure by means of frictional
resistance to flow and heated to compensate for the heat of vaporization.

Separator:

At the end of the pipe is a vessel or a wider section of pipe, sized to

allow almost complete separation of vapor and liquid. This separation is carried

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out at a pressure low enough to at least reduce the water content to the level
where the polymer can be pelletized. The separator is heated to maintain the
polymer in the molten state and to establish an optimum temperature, typically
between about 270° C and 285°C, to accomplish further removal of dissolved
moisture without causing undue degradation of the polymer. Separator is
preferably agitated to enhance further removal of dissolved moisture and to
provide blending. Operating the separator under vacuum will further increase the
molecular weight of the polyamide product. The polyamide product 45 removed
from the separator can be pelletized using methods known as strand casting.
IV. EQUIPMENT UTILIZED:

Table 6.20. List of major equipment for Multistage Distillation Column Reactor

EQUIPMENTS:
1 STORAGE TANK
2 EVAPORATOR
3 TURBULAR REACTOR
4 FRACTIONATION COLUMN
5 COOLER
6 PUMP
7 MULTI-STAGE DISTILLATION COLUMN REACTOR
8 MIXER
9 SEPARATOR

PROCESS FLOW DIAGRAM

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Figure 6.10 Process Floe Diagram for Multistage Distillation Column Reactor

V. RAW MATERIALS:

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Ammonia ( N H 3 ¿

Ammonia is an inorganic compound composed of a single nitrogen atom

covalently bonded to three hydrogen atoms that is an amidase inhibitor and
neurotoxin. It is both manufactured and produced naturally from bacterial
processes and the breakdown of organic matter. Ammonia is used in many
industrial processes, and as a fertilizer and refrigerant. It is characterized as a
colorless gas or compressed liquid with a pungent odor and exposure occurs by
inhalation, ingestion, or contact. Ammonia occurs naturally and is produced by
human activity. It is an important source of nitrogen which is needed by plants
and animals. Ammonia is a colorless gas with a very distinct odor. This odor is
familiar to many people because ammonia is used in smelling salts, many
household and industrial cleaners, and window-cleaning products. Ammonia gas
can be dissolved in water. This kind of ammonia is called liquid ammonia or
aqueous ammonia. Once exposed to open air, liquid ammonia quickly turns into
a gas. Ammonia is applied directly into soil on farm fields, and is used to make
fertilizers for farm crops, lawns, and plants. Many household and industrial
cleaners contain ammonia.

Figure 6.11: Ammonia

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Hexamethylene Diamine

Hexamethylene Diamine, also known as 1, 6-Hexanediamine, is an

organic compound that can appear as a clear colourless liquid or a colourless
crystalline solid. It derives from a hydride of a hexane.  Hexamethylene Diamine
is widely used for the production of polymers, it can be used as a reagent used to
modify acrylonitrile copolymers and to polycondense with compounds such as
calcein. It can be used as a reactant for the synthesis of dialkyl hexamethylene-
1,6-dicarbamate with alkyl carbamate in the presence of various metal catalysts
via the transesterification reaction, surface modifier for chlorinated and
fluorinated nanodiamond synthesized by detonation and reactant with adipic acid
for the synthesis of nylon 6-6 by polycondensation.

Figure 6.12: Hexamethylene Diamine (Solid)

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Water (H2O)

Water is an oxygen hydride consisting of an oxygen atom that is

covalently bonded to two hydrogen atoms. It has a role as an amphiprotic
solvent, a member of greenhouse gas, a human metabolite, a Saccharomyces
cerevisiae metabolite, an Escherichia coli metabolite and a mouse metabolite. It
is an oxygen hydride, a mononuclear parent hydride and an
inorganic hydroxy compound. It is a conjugate base of an oxonium. It is a
conjugate acid of a hydroxide. Water (chemical formula: H2O) is a transparent
fluid which forms the world's streams, lakes, oceans and rain, and is the major
constituent of the fluids of organisms. As a chemical compound, a water
molecule contains one oxygen and two hydrogen atoms that are connected by
covalent bonds. Water is a liquid at standard ambient temperature and pressure,
but it often co-exists on Earth with its solid state, ice; and gaseous state, steam
(water vapor).

Figure 6.13: Water (H2O)

Adipic Acid (C 6 H 10 O 4 ¿

Adipic acid is a white crystalline solid. It is insoluble in water. The primary

hazard is the threat to the environment. Immediate steps should be taken to limit
its spread to the environment. It is used to make plastics and foams and for other

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uses. Adipic acid or hexanedioic acid is the organic compound with

the formula (CH2)4(COOH)2. From an industrial perspective, it is the most
important dicarboxylic acid.

Figure 6.14: Adipic Acid

VI. SUSTAINABILITY:

Availability of Raw Materials:

The raw materials for this process are already available in the Philippines
and it consists of Hexamethylene Adipamide, Ammonia, Water and Adipic
Acid. The availability of the raw materials will greatly affect the process for
continuous procedure.

Table 6.21: Supplier of Raw Materials for Multistage Distillation Column Reactor
Process

RAW MATERIAL SUPPLIER

1 Hexamethylene EURO CHEMICALS INC.
Lot 2 Arty II, Corner Road 1, Brgy Mindanao
Adipamide Avenue, Quezon City, Metro Manila
Website: [Link]
Landline: (02) 8930 4715
Distance from Plant: 90.8 (94 min)
2 Ammonia Air Liquide Philippines
12th Floor Ecotower 32nd St corner, 9th Ave,
Taguig, Kalakhang Maynila
Website: [Link]/

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Landline: (02) 8838 1780

Distance from Plant: 112 km (120 min)
3 Adipic Acid Chasechem Industries, Inc.
5072 Filmore St, Makati, Metro Manila
Website: [Link]/
Landline: (02) 8551 0368
Distance from Plant: 137 km (168 min)

DEMAND AND SUPPLY OF RAW MATERIALS

Ammonia

The global ammonia market size was worth 48.65 billion USD in 2016.
The rising demand for ammonia in the fertilizer industry is expected to boost
industry growth. The product is also the building block for the world nitrogen
industry. Globally the demand & supply ratio of the product is anticipated to
move toward surplus, as the capacity addition is continuing to outpace
consumption, resulting in declining utilization rates. This capacity addition is
mostly increasing in the regions where the production cost is low and
availability of the raw material. Asia Pacific was the major producer and
consumer of ammonia in 2016. China is the largest producer of the product and
the country’s market is anticipated to ascend at a CAGR of 6.3% from 2017 to
2025. In China, ammonia is mostly produced from coal gasification, whereas
globally it is mostly obtained from natural gas. In terms of production, China is
followed by India and Indonesia. Globally, the capacity is anticipated to increase
significantly. The major capacity addition is projected to be in the Middle East
& Africa, Central & South America, and Southeast Asia. The largest addition is
anticipated to be in Indonesia and China.

The U.S. is among the major producers of ammonia globally. The

country had over 13 companies that produced the product at their 20 production
plants in 2015. In the U.S., approximately 45% of the product is consumed in
nitrogen fertilizer and the remaining is used for producing synthetic fibers
plastics, resins, and various other chemical compounds. As the natural gas

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accounts for around 50% of the production cost for nitrogen fertilizer, the
availability of cheap natural gas in the country is expected to be a major driving
factor for industry growth in the region. The global market is highly competitive
in nature and is currently witnessing constant price fluctuations. The industry is
marked by the presence of global as well as regional market players. The global
players are investing in the research & development activities for innovating
new and developed processes.

Figure 6.15: World Consumption of Ammonia 2014-2025

Source: [Link]

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Hexamethylene Diamine

The Hexamethylenediamine Market was valued at 5.98 Billion USD in

2018 and is projected to register at 5.65% during the forecast period. The Global
Hexamethylenediamine Market has been analyzed for five major regions,
namely, North America, Asia-Pacific, Europe, Latin America, and the Middle
East & Africa. The market in Asia-Pacific dominates the global
hexamethylenediamine market and is projected to register the highest CAGR
during the forecast period owing to the rapid industrialization in the region. The
increased use of hexamethylenediamine as a precursor to producing nylon 6, 6 in
end-use industries, such as automotive and textile, is expected to drive the
regional market demand. China is the largest consumer in the region on account
of rising exports of nylon from the country. For instance, in 2018, the total nylon
exports from China were valued at USD 137.70 million. Thus, making it among
the top three global nylon exporters. Furthermore, India and other South-East
Asian countries are propelling the regional market growth on account of the
increasing use of the product in the water treatment industry. These factors
create numerous opportunities for the players operating in the
hexamethylenediamine market in the region.

The market in North America accounted for a substantial market share in

2018. The growing demand for hexamethylenediamine as a raw material in the
paints and coating industry and the increasing constructional activities in the
region are driving the growth of the regional market. In addition, the rising
advancements in the US, coupled with emerging multifunctional applications
such as in 3D printing and functional coatings, are further driving the regional
market growth. The market in Europe is expected to showcase significant
growth during the forecast period. This can be attributed to the increasing use of
hexamethylenediamine to manufacture automotive components and produce
lubricants. The markets in Latin America and the Middle East & Africa are

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expected to show healthy growth during the forecast period owing to the
growing paints and coatings industry. The increasing use of HMDA in the
petrochemical industry is further fueling regional market growth.

Figure 6.16: Global Hexamethylenediamine Market Share

Source: [Link]

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Adipic Acid

The global adipic acid market size was valued at 5.56 billion USD in
2016 and is expected to develop at 4.7% over the forecast period. The market is
driven by increasing demand for lightweight and durable products in the
automotive, construction, and electronics industries. Rapidly expanding the
global construction industry is also projected to drive the product demand in
building components such as exterior panels, insulation materials, and housing
electronics. Growing automotive and packaging industries are also contributing
toward market growth. Asia Pacific holds excellent potential for market
penetration as adipic acid’s supply in this region is disrupted owing to low spot
prices. Adipic acid manufacturers are capitalizing on cheap, abundant raw
material currently present in the market. However, it may result in
overutilization, therefore bringing down the prices.

North America is one of the major supply hubs for engineered polymers,
therefore, making it a potential destination for adipic acid. North America’s
adipic acid demand was estimated to be around 858.6 kilo tons in 2015 and is
estimated to grow further at a rate of 2.6% over the forecast period. Growing
automobile industry in this region is likely to be the major factor for market
growth. The Asia Pacific market is exhibiting a significant potential for adipic
acid manufacturers to set up base in this region owing to the business-friendly
atmosphere. The product demand in this region is expected to reach 1,551.8 kilo
tons by the end of the forecast period. Adipic acid manufacturers are currently
strategizing to physically position themselves between raw material supply hub
and end-use industries to attain optimum growth and profit margin. Adhesive
and sealant manufacturers are moving manufacturing bases near the adipic acid
supply hub is one of the significant trends in the industry. These moves are
hinted towards attaining supply efficiency.

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Figure 6.17: World Consumption of Adipic Acid

Source: [Link]

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VII. PLANT ECONOMY

The total capital investment and annual cost production for the
Multistage Distillation Column Reactor process is calculated in this section.

EQUIPMENT COST

The method used to calculate the estimated capital cost for the
Production of Polyhexamethylene Adipamide from Adiponitrile via Multistage
Distillation Column Reactor is Lang method. The Lang factors were taken from
the Perry’s Chemical Engineering Handbook 8th Edition and the method used
depends on the type of processing equipment.

Table 6.22: Lang Factors (Green and Perry 2008)

Type of Plant Lang Factors

Fixed Capital Total Capital
Investment Investment
Solid Processing 4 4.7
Solid Fluid Processing 4.3 5
Fluid Processing 5 6

Formula for the computation of Fixed Capital Cost was taken from Chemical
Engineering Design Volume 6 by Coulson and Richardson.
C f =f L Ce

Where, C f = fixed capital cost

f L = “Lang Factor” which depends on the process type

Ce = total delivered cost of all the major equipment items

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Assuming the equipment delivery charge is 5% of the purchased equipment cost.

Table 6.23: Cost of Equipment for Multi-Distillation Column Reactor

EQUIPMENT QTTY. EQUIPMENT DELIVERED PEC = DEC X

COST (PHP) EQUIPMENT FACTOR
COST
Storage Tank 3 ₱219,105 ₱230,060.25 ₱1,150,301.25
Evaporator 1 ₱486,900 ₱511,245.00 ₱2,556,225.00
Tubular 1 ₱3,651,750 ₱3,834,337.50 ₱19,171,687.5
Reactor
Fractionation 1 ₱2,726,640 ₱2,862,972.00 ₱14,314,860.
Column
Cooler 1 ₱730,350 ₱766,867.50 ₱3,834,337.50
Pump 2 ₱973,800 ₱1,022,490.00 ₱5,112,450.00
Multi Stage 1 ₱7,303,500 ₱7,668,675.00 ₱38,343,375
Distillation
Column
Reactor
Mixer 1 ₱243,450 ₱255,622.50 ₱1,278,112.50
Separator 1 ₱219,105 ₱230,060.25 ₱1,150,301.25
Heater 1 ₱389,520 ₱408,996.00 ₱2,044,980.00
Reservoir 1 ₱2,434,500 ₱2,556,225.00 ₱12,781,125
Total 14 ₱19,378,620 ₱20,347,551.00 ₱101,737,755
Purchased
Cost of
Equipment:

Source: Alibaba

PROJECT COST

The project fixed capital cost necessary for the production of poly-
hexamethylene adipamide from adiponitrile via multi-stage distillation column
reactor was calculated using the typical factors for estimation of project’s capital
cost from Chemical Engineering Design.

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Table 6.24: Typical factors for Estimation of Project’s Fixed Capital Cost

Process Type
Item
Fluid Fluids-Solids Solids
1. Major Equipment,
PCE PCE PCE
Total Purchase Cost
f1 Equipment
0.4 0.45 0.5
Erection
f2 Piping 0.7 0.45 0.2
f3 Instrumentation 0.2 0.15 0.1
f4 Electrical 0.1 0.1 0.1
f5 Buildings, process 0.15 0.1 0.05
*f6 Utilities 0.5 0.45 0.25
*f7 Storages 0.15 0.2 0.25
*f8 Site Development 0.05 0.05 0.05
*f9 Ancillary
0.15 0.2 0.3
Building
2. Total physical
Plant Cost (PPC)
PPC = PCE (1+f1+ 3.4 3.15 2.8
……+ f9)
PCEx
f10 Design and
0.3 0.25 0.2
Engineering
f11 Contractor’s Fee 0.05 0.05 0.05
f12 Contingency 0.1 0.1 0.1
3. Fixed Capital =
PPC (1+ f10 +f11 + f12) 1.45 1.4 1.35
PPC
Adapted from Coulson and Richardson, Chemical Engineering Design, Volume 6

Physical Plant Cost (PPC)

Physical Plant Cost = (PCE) (1+f1+……+ f9)

PPC = ₱101,737,755.00 (3.15)

PPC = ₱ 320,473,928.25

Fixed Capital Cost (FCC)

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Fixed Capital Cost = (PPC) (1.4)

FCC = ₱ 320,473,928.25 (1.4)

FCC = ₱448,663,499.55

Working Capital Cost (WCC)

Working Capital Cost = (FCC) (0.05)

WCC = ₱448,663,499.55 (0.05)

WCC = ₱ 22,433,174.98

Total Capital Investment

Total Capital Investment = FCC + WCC

TCI = ₱448,663,499.55 + ₱ 22,433,174.98

TCI = ₱ 471,096,674.53

FIXED COST, VARIABLE COST, AND OTHER COST

The operating cost that is used for the production of poly-hexamethylene

adipamide from adiponitrile via multi-stage distillation column reactor was
calculated using costing and project evaluation from Chemical Engineering
Design, volume 6.

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Figure 6.18: Costing and Project Evaluation

Source: Peter and Timmerhaus

FIXED COSTS

Maintenance Cost (MC)

Maintenance Cost: FCC (0.10)

MC: ₱448,663,499.55 (0.10)

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MC: ₱ 44,866,349.96

OPERATING LABOR COST

For plant capacity of 200 MT per day and for an average condition, the
estimated operating labor equipment is 50 employee-hours/day/processing step
day considering the three processing steps and 300 days operating time per year.
The estimated operating labor requirement was estimated using Figure 6.1.2.

Figure 6.19: Operating Labor Requirements

Table 6.25: Summary of Current Regional Daily Minimum Wages Rates

Region SECTOR
IV-A Non-agriculture Agriculture
Plantation Non-Plantation
400 372 372
Source: Department of Labor and Employment 2020

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Operating Labor Cost = Operating Labor x Operating Time x Wage x Processing

Steps

OLC:

55 employee−hours 300 working days P 400

x x
day −processing year employee−8 hr

x 3 processing x 1 year operation

OLC: ₱ 2,475,000.00

Laboratory Cost (LC)

Laboratory cost: (OLC) (0.23)

Laboratory Cost: ₱ 2,475,000.00 (0.23)

LC: ₱ 569,250.00

Supervision Cost (SC)

Supervision Cost: (OLC) (0.20)

Supervision Cost: ₱ 2,475,000.00 (0.20)

SC: ₱ 495,000.00

Plant Overheads (PO)

Plant overheads: (OLC) (0.50)

Plant Overheads: ₱ 2,475,000.00 (0.50)

PO: ₱ 1,237,500.00

Capital Charges (CC)

Capital Charges = (FCC) (0.10)

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Capital Charges = ₱448,663,499.55 (0.10)

CC = ₱ 44,866,349.96

Local Taxes (LT)

Local Taxes = (FCC) (0.02)

Local Taxes = ₱448,663,499.55 (0.02)

LT = ₱ 8,973,269.99

Insurance (I)

Insurance = (FCC) (0.01)

Insurance = ₱448,663,499.55 (0.01)

I = ₱ 4,486,635.00

License Fee / Royalty Fee (LF/RF)

License Fee / Royalty Fee = (FCC) (0.01)

License Fee / Royalty Fee = ₱448,663,499.55 (0.01)

(LF/RF) = ₱ 4,486,635.00

Table 6.26: Summary of Fixed Cost for Multi-stage Distillation Column Reactor

FIXED COSTS
Maintenance Cost ₱ 44,866,349.96
Operating Labor Cost ₱ 2,475,000.00
Laboratory Cost ₱ 569,250.00
Supervision Cost ₱ 495,000.00
Plant Overheads ₱ 1,237,500.00
Capital Charges ₱ 44,866,349.96

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Local Taxes ₱ 8,973,269.99

Insurance ₱ 4,486,635.00
License Fee/Royalty Fees ₱ 4,486,635.00
TOTAL FIXED COST ₱ 112,455,989.89

VARIABLE COSTS

Miscellaneous Operating Materials (MOM)

Miscellaneous Operating Materials = (Maintenance Cost) (0.10)

Miscellaneous Operating Materials = ₱ 44,866,349.96 (0.10)

MOM: ₱ 4,486,635.00

RAW MATERIAL COST:

Table 6.27: Raw Material for Multi-stage Distillation Column Reactor

Raw Material Cost (PHP/10 MT)

Ammonia ₱ 773,067.00
Adipic Acid ₱ 1,558,569.00
HMDA ₱ 258,057.00
TOTAL: ₱ 2,589,693.00

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Table 6.28: Summary of Variable Cost for Multi-stage Distillation Column Reactor

VARIABLE COSTS

Miscellaneous Operating Materials ₱ 4,486,635.00

Raw Materials Cost ₱ 2,589,693.00

TOTAL VARIABLE COST ₱ 7,076,328.00

DIRECT PRODUCTION COST (DPC)

Direct Production Cost = VC + TFC

Direct Production Cost = ₱ 7,076,328.00 + ₱ 112,455,989.89

DPC = ₱ 119,532,317.89

OTHER COSTS

Sales Expense (SE)

Sales Expense = Direct Production Cost (0.20)

Sales Expense = ₱ 119,532,317.89 (0.20)

SE = ₱ 23,906,463.58

General Overheads (GO)

General Overheads = (DPC) (0.25)

General Overheads = ₱ 119,532,317.89 (0.25)

GO = ₱ 29,883,079.47

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Research and Development (R&D)

Research and Development = (DPC) (0.28)

Research and Development = ₱ 119,532,317.89 (0.28)

R&D = ₱ 33,469,049.01

Table 6.29: Summary of Other Costs for Multi-stage Distillation Column

Reactor

OTHER COSTS
SE ₱ 23,906,463.58
GO ₱ 29,883,079.47
R&D ₱ 33,469,049.01
TOTAL OTHER COST ₱ 87,258,592.06

ANNUAL PRODUCTION COST (APC)

Annual Production Cost = DPC + OC

Annual Production Cost = ₱ 119,098,067.89 + ₱ 87,258,592.06

APC = ₱ 206,790,909.95

PRODUCTION COST:

Annual Production Cost

Production Cost = Plant capacity days
( day )
(300 working
year
)

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₱ 206,790,909.95
Production Cost = 200 MT days
( )(300 working )
day year

Production Cost = ₱ 3,346.52.99

VIII. MANUFACTURABILITY

PURITY

The Polyhexamethylene Adipamide obtain from the Multi-stage

Distillation Column Reactor Process has a purity of 80%. (nylon%[Link])

YIELD

The Polyhexamethylene Adipamide obtain from the Multi-stage

Distillation Column Reactor Process has a yield 55%. (nylon%[Link])

PROCESS USAGE

The Production of Polyhexamethylene Adipamide from Adiponitrile via

Multi-stage Distillation Column Reactor Process is not being used.

IX. SAFETY

Table 6.30 – Parameters for Multistage Distillation Column Reactor Process

PARAMETERS RANGE
Temperature 280 ºC

Pressure 2 atm

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TOXILOGICAL RATING

The toxicity of raw materials is examined based on the health hazards

level that can harm people. The health hazards of the raw material are based
from the Material Safety Data Sheet and the table below was used to evaluate
the toxicity level.

Table 6.31: Health Hazard rating for Multi-stage Distillation Column Reactor Process

HEALTH 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

3 For serious hazard, major injury likely unless prompt action is taken,
medical treatment given

4 For severe hazard, life-threatening, major of permanent damage may

result from single or repeated exposures

Table 6.32: Toxicity Level Scores of Raw Materials and Products for Multi-stage
Distillation Column Reactor Process

Criteria Weigh Major Raw Materials Product

t

Ammonia Adipic Hexamethylene Nylon 6,6

Acid Diamine

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Severity of 0.1 4 2 4 0
Immediate
Effects
Sensitization 0.1 4 2 4 1
Level

Carcinogenicit 0.3 0 0 0 1
y Level

Reproduce 0.25 3 0 3 0
Toxicity Level

Severity of 0.25 4 2 4 1
Chronic Effects

Weighted Score 2.55 0.9 2.55 0

Average 1.66
Weighted Score

Table 6.33: Basis of Toxicity Level Scores for Raw Materials for Multi-stage
Distillation Column Reactor Process

Criteria Raw Materials

Ammonia Adipic Acid Hexamethylene

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Diamine

Severity of May cause eye May cause eye May cause eye
Immediate irritation and irritation and irritation, skin
Effects skin damage skin damage damage and difficulty
in breathing
Sensitization Irritant Irritant Irritant
Level

Carcinogenicity Not listed as Not listed as Not listed as

Level carcinogen carcinogen carcinogen

Reproduce Mutagenic Non- Mutagenic

Toxicity Level mutagenic

Severity of Lung damage Prolonged eye Prolonged eye and

Chronic Effects and death may and skin skin contact may
occur after contact may cause severe eye and
exposure to very cause severe skin damage and
high eye and skin difficulty in
concentration of damage. breathing.
ammonia.

Table 6.34: Basis of Toxicity Level Scores for Product for Multi-stage Distillation
Column Reactor Process

Criteria Product

Nylon 6,6

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Severity of Immediate May not cause skin, eye and lung

Effects damage

Sensitization Level Irritant

Carcinogenicity Level Carcinogenic in some aspects

Reproduce Toxicity Non-mutagenic

Level

Severity of Chronic May cause severe itchiness as

Effects textile.

X. ENVIRONMENTAL IMPACT

The basis for the environmental hazard for the Production of

Polyhexamethylene Adipamide from Adiponitrile via Multi-stage Distillation
Column Reactor Process is the raw materials and product. The environmental
hazard data is based on the harmful effects of the materials to the environment
and the table below was used to evaluate the toxicity level.

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Table 6.35: Environmental Hazard Rating

ENVIRONMENTAL HAZARD RATING

0 For minimal hazard and no significant risk to the environment

1 For slight hazard or minor reversible damage possible

2 For moderate hazard, temporary or minor damage may occur

3 For serious hazard, major damage to environment unless prompt action

is taken

4 For severe hazard, permanent damage may result

Table 6.36: Environmental Hazard Level Scores of Raw Materials and Products

Major Raw Materials Product

Criteria Weight
Adipic Nylon
Ammonia HMDA
Acid 6,6

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Aquatic Toxicity 0.2 3 0 2 0

Toxicity on Plants
0.25 3 0 3 0
and Animals
Toxicity of
Immediate 0.2 1 0 0 0
Degradation
Long-term
0.35 2 1 1 1
Degradation Effect
 
Weighted Score 2.25 0.35 1.5 1

Average Weighted  
1.275
Score

Table 6.37: Basis of Environmental Hazard Level Scores for Raw Materials

Criteria Raw Materials

Ammonia Adipic Acid Hexamethylene

Diamine

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Aquatic Toxicity Dangerous to No known Dangerous to

Aquatic Life toxic effects Aquatic Life

Toxicity on Plants Dangerous for No known Dangerous for

and Animals plants and animals toxic effects plants and animals

Toxicity of No known toxic No known No known toxic

Immediate effects toxic effects effects
Degradation

Long-term No known toxic No known No known toxic

Degradation Effect effects toxic effects effects

Table 6.38: Basis of Environmental Hazard Level Scores for Products

Criteria Product

Nylon 6,6

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Aquatic Toxicity No known toxic effects

Toxicity on Plants and Animals No known toxic effects

Toxicity of Immediate Degradation No known toxic effects

Long-term Degradation Effect No known toxic effects

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PROCESS 3
PRODUCTION OF
POLYHEXAMETHYLE
NE ADIPAMIDE
(NYLON 6,6) FROM
DIRECT SYNTHESIS
OF ADIPIC ACID

Production of Polyhexamethylene Adipamide (Nylon 6,6) from direct

synthesis of Adipic Acid

I. INTRODUCTION

Current preparation methods of high purity adipic acid are from

oxidation of cyclohexanone, cyclohexanol, cyclohexanone-cyclohexanol mixture
(KA oil). Nitric acid is used as the oxidant. Nitrous gases emissions formed from

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these processes contribute to global warming and ozone depletion. Direct

synthesis of adipic acid from cyclohexene has been developed. The oxidation
reaction creates acidic conditions which causes the direct conversion of
cyclohexenes to adipic acid. Crystallized adipic acid is collected from filtration
shows a pure 90% yield. The remaining aqueous reaction solution can be reused
with renewed hydrogen peroxide to produce 78% yield.
Different catalyst is used - H2WO4 in Bronsted acidic ionic liquids under
solvent-free conditions (Wang, 2017). The yield of adipic acid was 96%. The
catalytic system can be easily recovered and reused for four reaction runs
without significant loss of catalytic activity. Simple operation of the catalyst
system and avoidance of the emission of nitrous oxide are the benefits of this
work.

II. REACTION MECHANISM

C 6 H 10 +4 H 2 O 2 → C 6 H 10 O 4 +4 H 2 O

C 6 H 10 O 4 +C 6 H 16 N 2 → C12 H 22 N 2 O2 +2 H 2 O

III. PROCESS DESCRIPTION

Oxidation of cyclohexene

Oxidation of cyclohexene takes place in a continuous process with micro

reaction technology. The micro reactor (R-101) deals with limits in interfacial
transfer, controls safe use of hydrogen peroxide, and observes for better
selectivity under decreased reaction times. 30% hydrogen peroxide ( H ¿ ¿ 2 O2)¿

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is used as the oxidant with Na2 WO2 and ¿ ¿ as a phase-transfer catalyst (PTC).
The aqueous, organic biphasic reaction gives a high yield of 93% without
presence of organic solvents and halides. The use of oxidant hydrogen peroxide
( H ¿ ¿ 2 O2) ¿ produces water being the sole by-product of the reaction.

Recovery of cyclohexene

Cyclohexene oxidation products flow to the separator (SEP-101) where

vapor proceeds to the distillation column (D-101) and liquid flows to the crude
crystallizer (CR-101). Cyclohexene is recycled back to cyclohexene pump (P-
101 A/B) through a condenser (H-101). The distillation bottoms, mostly water,
are released.

Treatment of crude products

Crude oil product proceeds to a series of crystallizers (CR-101, CR-102)

and centrifuge (CE-101, CE-102). Impurities are removed from the oil. Large
amount of water is evaporated from the concentrating still (D-102). The outlet
stream from the last centrifuge (CE-102) is sent to a dryer (HE-101) producing
the solid adipic acid.

Nylon 6,6 Formation

The adipic acid proceeds to the steam-supplied mixer (R-102) where

hexamethylene diamine and acetic acid are fed. The pH is set at 7.8 to form
Nylon salt. The salt proceeds to the autoclave (R-103) after being concentrated
under vacuum. The autoclave temperature is increased to 280℃ to remove the
rest of the water. The final product is extruded (RO-101) as ribbons onto chilling
rolls. Chips from the chopper (NC-101) are melted (HET-102) after filtration
(HET-101) to produce the nylon fibers.
IV. EQUIPMENT UTILIZED

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Table 6.39. List of Equipment from direct synthesis of Adipic Acid

EQUIPMENT
1 Cyclohexene Pump
2 H2O2 and Catalyst Pump
3 Microreactor
4 Separator
5 Distillation column
6 D-101 Condenser
7 D-101 Reboiler
8 Crude Crystallizer
9 CR-101 Reboiler
10 Centrifuge 1
11 Concentrating Still
12 D-102 Condenser
13 D-102 Reboiler
14 Refined Crystallizer
15 CR-102 Reboiler
16 Centrifuge 2
17 Adipic Acid Dryer
18 Reactor Mixer
19 Autoclave
20 Autoclave Valve
21 Polymerization Reactor
22 Casting Roll
23 Nylon Chopper
24 Nylon Resin Tank
25 Melt Tank
26 Melt Spinning Machine

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PROCESS FLOW DIAGRAM

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Figure 6.20: Production of Polyhexamethylene Adipamide from direct synthesis of Adipic

Acid

V. RAW MATERIALS:

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Cyclohexene (C ¿ ¿ 6 H 10) ¿

Cyclohexene is a hydrocarbon with the formula C₆H₁₀. This

cycloalkene is a colorless liquid with a sharp smell. It is an intermediate in
various industrial processes. Cyclohexene is not very stable upon long term
storage with exposure to light and air because it forms peroxides.

Figure 6.21: Cyclohexene

Hydrogen Peroxide ( H ¿ ¿ 2 O2)¿

Hydrogen peroxide is a chemical compound with the formula H₂O₂. In

its pure form, it is a very pale blue liquid, slightly more viscous than water. It is
used as an oxidizer, bleaching agent, and antiseptic.

Figure 6.22: 30% Hydrogen Peroxide solution

Acetic Acid (CH ¿¿ 3COOH )¿

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Acetic acid, systematically named ethanoic acid, is a colorless liquid

organic compound with the chemical formula CH₃COOH. When undiluted, it is
sometimes called glacial acetic acid. Vinegar is no less than 4% acetic acid by
volume, making acetic acid the main component of vinegar apart from water.

Figure 6.23: Acetic acid

Hexamethylene Diamine

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Hexamethylene Diamine, also known as 1, 6-Hexanediamine, is an

organic compound that can appear as a clear colorless liquid or a colorless
crystalline solid. It derives from a hydride of a hexane.
Hexamethylene Diamine is widely used to produce polymers, it can be
used as a reagent used to modify acrylonitrile copolymers and to polycondense
with compounds such as calcein.

Figure 6.24: Hexamethylene Diamine (Solid)

Water (H2O)

Water is an oxygen hydride consisting of an oxygen atom that is

covalently bonded to two hydrogen atoms. It has a role as an amphiprotic
solvent, a member of greenhouse gas, a human metabolite, a Saccharomyces
cerevisiae metabolite, an Escherichia coli metabolite, and a mouse metabolite. It
is an oxygen hydride, a mononuclear parent hydride and an
inorganic hydroxy compound. It is a conjugate base of an oxonium. It is a
conjugate acid of a hydroxide. Water (chemical formula: H2O) is a transparent
fluid which forms the world's streams, lakes, oceans, and rain, and is the major
constituent of the fluids of organisms. As a chemical compound, a water
molecule contains one oxygen and two hydrogen atoms that are connected by

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covalent bonds. Water is a liquid at standard ambient temperature and pressure,

but it often co-exists on Earth with its solid state, ice; and gaseous state, steam
(water vapor).

Figure 6.25: Water (H2O)

VI. SUSTAINABILITY:

Availability of Raw Materials:

The raw materials for this process are already available in the Philippines
and it consists of Hexamethylene Adipamide, Acetic Acid, Hydrogen Peroxide,
Cyclohexene and water. The availability of the raw materials will greatly affect
the process for continuous procedure of the direct synthesis.

RAW MATERIAL SUPPLIER

1 Cyclohexene J.E MANALO & CO., INC
1188 Bernal Street, Pasig, 1609 Metro Manila
Website: [Link]/
Landline: (02) 641-2796 – 98
Distance from Plant: 136 km (164 min)
2 Acetic Acid BRENNTAG INGREDIENTS INC.
16th Floor Asian Star Building, Muntinlupa.
Metro Manila
Website: [Link]/
Landline: (02) 8812 9385
Distance from Plant: 155 km (180 min)

3 Hydrogen Peroxide SBS PHILIPPINES CORPORATION

10 Rest Haven, San Francisco del Monte,
Quezon City, 1105 Metro Manila

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Website: [Link]/
Landline: (02) 8371 1111
Distance from Plant:120 km (120 min)
4 Hexamethylene EURO CHEMICALS INC.
Lot 2 Arty II, Corner Road 1, Brgy Mindanao
Adipamide Avenue, Quezon City, Metro Manila
Website: [Link]
Landline: (02) 8930 4715
Distance from Plant: 90.8 (94 min)

DEMAND AND SUPPLY OF RAW MATERIALS

Cyclohexene

In 2017, the global Cyclohexene market is led by Japan, capturing about

48.89% of global Cyclohexene production. China is the second-largest region-
wise market with 35.99% of production share. At present, the major
manufacturers of Cyclohexene are Asahi Kasei, Shenma Group, Chemoxy,
Gelest, Metadynea Austria. Asahi Kasei is the world leader, holding 40.59%
production market share in 2017. In the future, global market is expected to
witness significant growth on account of rising applications, so in the next few
years, Cyclohexene production will show a trend of steady growth. The global
Cyclohexene (CAS 110-83-8) market is valued at 381.3 million USD in 2020 is
expected to reach 441.8 million USD by the end of 2026, growing at a CAGR of
2.1% during 2021-2026.

The research report has incorporated the analysis of different factors that
augment the markets growth. It constitutes trends, restraints, and drivers that
transform the market in either a positive or negative manner. This section also
provides the scope of different segments and applications that can potentially
influence the market in the future. The detailed information is based on current
trends and historic milestones. This section also provides an analysis of the
volume of production about the global market and also about each type from

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2015 to 2026. This section mentions the volume of production by region from
2015 to 2026. Pricing analysis is included in the report according to each type
from the year 2015 to 2026, manufacturer from 2015 to 2020, region from 2015
to 2020, and global price from 2015 to 2026.

Figure 6.26: World Consumption of Cyclohexene

Source: [Link]

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Acetic Acid

The global acetic acid market size was valued at 8.92 billion USD in
2019 and is expected to grow at a compound annual growth rate of 5.2% from
2020 to 2027. Rising demand for the product from Vinyl Acetate
Monomer (VAM) producers worldwide is projected to remain a key driving
factor for the market growth. VAM consumes a majority of the acetic acid
produced worldwide. Asia Pacific dominated the market and accounted for
62.0% of the global revenue in 2019. This is attributed to the increasing
penetration of polymer formulators in the region. Acetic acid is a key substance
used across an array of industries across China, Japan, and India. The region is
witnessing high construction activities due to increased mergers and
acquisitions. Since the past decade, the region has been home to a number of
multinational companies from all business domains and has reflected multiple
manufacturing expansion projects.

In the Asia Pacific region, prices for plastics and polymers were stable,
despite slight trade tension between China and the U.S. With more growing
industries across countries such as China, Japan, and India, the demand for
plastics and plastic products increased. PTA demand reflected a significant rise
over the past decade which directly reflects the increasing consumption of acetic
acid in the region. The European region reflected significant progress in the food
& beverage industry in 2018, with a turnover generation of USD 1,194 billion. It
is recognized as the largest manufacturing industry in the European Union
employing over 4.57 million people. Increasing requirements for packaged food
across countries such as Germany, France, Italy, and the U.K., led to increasing
demand for acetic acid in the region significantly. Moreover, the growing food
industry also led to high demand for packaging which is anticipated to fuel the
demand for acetic acid. The North American market is driven by increasing
demand for ethanol across an array of industries. More than 90% of the
substance, in the U.S., is formulated from corn grain to ensure positive energy

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balance. Further, the U.S. automotive sector reflected inclination towards the use
of E85 gas, which is typically a mixture of 15% gasoline and 85% ethanol. This
is likely to increase the consumption of acetic acid in ethanol production in the
country.

Figure 6.27: World consumption of Acetic Acid

Source: [Link]

Hydrogen Peroxide

The global hydrogen peroxide market size was valued at 1.49 billion
USD in 2019 and is expected to grow at a compound annual growth rate of 4.7%
from 2020 to 2027. Rising demand for the product from the healthcare industry
due to its antiseptic properties is projected to remain a key factor fueling market
growth. In the healthcare sector, the product is highly demanded as an antiseptic,
which is traditionally utilized on skin cuts and bruises to prevent infections. It is
also widely used as a mouth rinse as it has the ability to relieve mouth irritation
or mucus and other oral infections. Majorly, the substance releases oxygen,
which leads to foaming on the bruised and cut skin and eventually leads to
effective removal of dead skin as well as keeps the wound safe from infection.

Furthermore, in light of the recent COVID-19 pandemic, demand for

hydrogen peroxide has grown significantly worldwide due to its high

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consumption in formulation of disinfectant products. According to multiple

guidelines issued by governments across the globe, disinfecting public as well as
private spaces is extremely necessary to subside the impact of the coronavirus
spread. Public areas such as commercial buildings, public stoppages, airports,
and railway platforms need to be sterilized for over 60 minutes within closed
boundaries. Similar household cleaning protocols have also been issued by
several governments and therefore demand for sanitizers and disinfectant
products have reflected noteworthy growth.

The Asia Pacific led the market and accounted for 39.5% share of the
global revenue in 2019. This is attributed to increasing penetration of chemical
formulators, personal care products, and medical industries in the region. China,
India, Thailand, South Korea, and Japan have turned into major hubs for
multinationals operating in these domains to establish their business practices in
the country due to lower land prices, availability of skilled labor, and increased
trade balance. North America is observed to be leading the wastewater treatment
industry due to persistence of prolonged water-borne illness in the country. U.S.
treats more than 34 billion gallons of toxic water on a daily basis for safe
consumption by the local residents. Removal of phosphorus and nitrogen from
the water sources, coupled with oxidation of wastewater, is one of the key
requirements prevalent in the country, which has eventually led to high
consumption of hydrogen peroxide across the industry in the country.

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Figure 6.28: World consumption of Hydrogen Peroxide

Source: [Link]

Hexamethylene Diamine

The Hexamethylenediamine Market was valued at 5.98 Billion USD in

2018 and is projected to register at 5.65% during the forecast period. The Global
Hexamethylenediamine Market has been analyzed for five major regions,
namely, North America, Asia-Pacific, Europe, Latin America, and the Middle
East & Africa. The market in Asia-Pacific dominates the global
hexamethylenediamine market and is projected to register the highest CAGR
during the forecast period owing to the rapid industrialization in the region. The
increased use of hexamethylenediamine as a precursor to producing nylon 6, 6 in
end-use industries, such as automotive and textile, is expected to drive the
regional market demand. China is the largest consumer in the region on account
of rising exports of nylon from the country. For instance, in 2018, the total nylon
exports from China were valued at USD 137.70 million. Thus, making it among
the top three global nylon exporters. Furthermore, India and other South-East
Asian countries are propelling the regional market growth on account of the
increasing use of the product in the water treatment industry. These factors

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create numerous opportunities for the players operating in the

hexamethylenediamine market in the region.

The market in North America accounted for a substantial market share in

2018. The growing demand for hexamethylenediamine as a raw material in the
paints and coating industry and the increasing constructional activities in the
region are driving the growth of the regional market. In addition, the rising
advancements in the US, coupled with emerging multifunctional applications
such as in 3D printing and functional coatings, are further driving the regional
market growth. The market in Europe is expected to showcase significant
growth during the forecast period. This can be attributed to the increasing use of
hexamethylenediamine to manufacture automotive components and produce
lubricants. The markets in Latin America and the Middle East & Africa are
expected to show healthy growth during the forecast period owing to the
growing paints and coatings industry. The increasing use of HMDA in the
petrochemical industry is further fueling regional market growth.

Figure 6.29: Global Hexamethylenediamine Market Share

Source: [Link]

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VII. PLANT ECONOMY

The total capital investment and annual cost production for the
production of Polyhexamethylene Adipamide from direct synthesis of Adipic
Acid process is calculated in this section.

EQUIPMENT COST

The method used to calculate the estimated capital cost for Production of
Polyhexamethylene Adipamide (Nylon 6,6) from direct synthesis of Adipic Acid
is Lang method. The Lang factors were taken from the Perry’s Chemical
Engineering Handbook 8th Edition and the method used depends on the type of
processing equipment.

Table 6.40: Lang Factors (Green and Perry)

Type of Plant Lang Factors

Fixed Capital Total Capital
Investment Investment
Solid Processing 4 4.7
Solid Fluid Processing 4.3 5
Fluid Processing 5 6

Formula for the computation of Fixed Capital Cost was taken from Chemical
Engineering Design Volume 6 by Coulson and Richardson.
C f =f L Ce

Where, C f = fixed capital cost

f L = “Lang Factor” which depends on the process type

Ce = total delivered cost of all the major equipment items

Assuming the equipment delivery charge is 5% of the purchased equipment cost.

Table 6.41: Cost of Equipment for Direct Synthesis of Adipic Acid

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EQUIPMENT QTTY. EQUIPMENT Delivered PEC = DEC

COST (PHP) Equipment X FACTOR
Cost
Pump 2 ₱ 87,642 ₱ 92,024.10 ₱ 460,120.50
Microreactor 1 ₱ 486,900 ₱ 511,245.00 ₱ 2,556,225
Separator 1 ₱ 102,249 ₱ 107,361.45 ₱ 536,807.25
Distillation 1 ₱ 2,434,500 ₱ 2,556,225.00 ₱ 12,781,125
column
Crude 2 ₱ 642,708 ₱ 674,843.40 ₱ 3,374,217
Crystallizer
CR-101 2 ₱ 486,900 ₱ 511,245.00 ₱ 2,556,225
Reboiler
Centrifuge 1 3 ₱ 2,629,260 ₱ 2,760,723.00 ₱ 13,803,615
Concentrating 2 ₱ 486,900 ₱ 511,245.00 ₱ 2,556,225
Still
D-102 2 ₱ 1,606,770 ₱ 1,687,108.50 ₱ 8,435,542.5
Condenser
Adipic Acid 1 ₱ 486,900 ₱ 511,245.00 ₱ 2,556,225
Dryer
Reactor Mixer 1 ₱ 97,380 ₱ 102,249.00 ₱ 511,245.00
Autoclave 1 ₱2,833,027.6 ₱ 2,974,679.03 ₱ 14,873,395
Polymerizatio 1 ₱1,460,700 ₱ 1,533,735.00 ₱ 7,668,675
n Reactor
Casting Roll 1 ₱ 2,434,500 ₱ 2,556,225.00 ₱ 12,781,125
Nylon 1 ₱ 243,450 ₱ 255,622.50 ₱ 1,278,112.5
Chopper
Nylon Resin 1 ₱ 29,214 ₱ 30,674.70 ₱ 153,373.5
Tank
Melt Tank 1 ₱ 48,690 ₱ 51,124.50 ₱ 255,622.50
Melt Spinning 1 ₱2,921,400 ₱ 3,067,470.00 ₱ 15,337,350
Machine
Autoclave 1 ₱ 24,345 ₱ 25,562.25 ₱ 127,811.25
Valve
Total 26 ₱19,543,435 ₱20,520,607.43 ₱102,603,037
Purchased
Cost of
Equipment:
Source: Alibaba

PROJECT COST

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The project fixed capital cost necessary for the production of

polyhexamethylene adipamide from direct synthesis of adipic acid was
calculated using the typical factors for estimation of project’s capital cost from
Chemical Engineering Design.

Table 6.42: Typical factors for Estimation of Project’s Fixed Capital Cost

Process Type
Item
Fluid Fluids-Solids Solids
1. Major Equipment,
PCE PCE PCE
Total Purchase Cost
f1 Equipment
0.4 0.45 0.5
Erection
f2 Piping 0.7 0.45 0.2
f3 Instrumentation 0.2 0.15 0.1
f4 Electrical 0.1 0.1 0.1
f5 Buildings, process 0.15 0.1 0.05
*f6 Utilities 0.5 0.45 0.25
*f7 Storages 0.15 0.2 0.25
*f8 Site Development 0.05 0.05 0.05
*f9 Ancillary
0.15 0.2 0.3
Building
2. Total physical
Plant Cost (PPC)
PPC = PCE (1+f1+ 3.4 3.15 2.8
……+ f9)
PCEx
f10 Design and
0.3 0.25 0.2
Engineering
f11 Contractor’s Fee 0.05 0.05 0.05
f12 Contingency 0.1 0.1 0.1
3. Fixed Capital =
PPC (1+ f10 +f11 + f12) 1.45 1.4 1.35
PPC
Adapted from Coulson and Richardson, Chemical Engineering Design, Volume 6

Physical Plant Cost (PPC)

Physical Plant Cost = (PCE) (1+f1+……+ f9)

PPC = ₱102,603,037.2 (3.15)

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PPC = ₱ 323,199,567.06

Fixed Capital Cost (FCC)

Fixed Capital Cost = (PPC) (1.4)

FCC = ₱ 323,199,567.06 (1.4)

FCC = ₱ 452,479,393.89

Working Capital Cost (WCC)

Working Capital Cost = (FCC) (0.05)

WCC = ₱ 452,479,393.89 (0.05)

WCC = ₱ 22,623,969.69

Total Capital Investment

Total Capital Investment = FCC + WCC

TCI = ₱ 452,479,393.89 + ₱ 22,623,969.69

TCI = ₱ 475,103,363.58

FIXED COST, VARIABLE COST, AND OTHER COST

The operating cost that is used for the production of polyhexamethylene

adipamide from direct synthesis of adipic acid was calculated using costing and
project evaluation from Chemical Engineering Design, volume 6.

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Figure 6.30: Costing and Project Evaluation

Source: Peter and Timmerhaus

FIXED COSTS

Maintenance Cost (MC)

Maintenance Cost: FCC (0.10)

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MC: ₱ 452,479,393.89 (0.10)

MC: ₱ 45,247,939.39

OPERATING LABOR COST

The estimated labor requirement for an average condition is 32

employees – hour per day considering the three processing steps and 300 days
operating time per year.

Figure 6.31: Operating Labor Requirements

Table 6.43: Summary of Current Regional Daily Minimum Wages Rates

Region SECTOR
IV-A Non-agriculture Agriculture
Plantation Non-Plantation
400 372 372

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Source: Department of Labor and Employment 2020

Operating Labor Cost = Operating Labor x Operating Time x Wage x Processing

Steps

OLC:

55 employee−hours 300 working days P 400

x x
day −processing year employee−8 hr

x 3 processing x 1 year operation

OLC: ₱ 2,475,000.00

Laboratory Cost (LC)

Laboratory cost: (OLC) (0.23)

Laboratory Cost: ₱ 2,475,000.00 (0.23)

LC: ₱ 569,250.00

Supervision Cost (SC)

Supervision Cost: (OLC) (0.20)

Supervision Cost: ₱ 2,475,000.00 (0.20)

SC: ₱ 495,000.00

Plant Overheads (PO)

Plant overheads: (OLC) (0.50)

Plant overheads: ₱ 2,475,000.00 (0.50)

PO: ₱ 1,237,500.00

Capital Charges (CC)

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Capital Charges = (FCC) (0.10)

Capital Charges = ₱452,479,393.89 (0.10)

CC = ₱ 45,247,939.39

Local Taxes (LT)

Local Taxes = (FCC) (0.02)

Local Taxes = ₱452,479,393.89 (0.02)

LT = ₱ 9,049,587.88

Insurance (I)

Insurance = (FCC) (0.01)

Insurance = ₱452,479,393.89 (0.01)

I = ₱ 4,524,793.94

License Fee / Royalty Fee (LF/RF)

License Fee / Royalty Fee = (FCC) (0.01)

License Fee / Royalty Fee = ₱452,479,393.89 (0.01)

(LF/RF) = ₱ 4,524,793.94

Table 6.44: Summary of Fixed Cost for Direct Synthesis of Adipic Acid

FIXED COSTS
Maintenance Cost ₱ 45,247,939.39
Operating Labor Cost ₱ 2,475,000.00
Laboratory Cost ₱ 569,250.00
Supervision Cost ₱ 495,000.00
Plant Overheads ₱ 1,237,500.00

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Capital Charges ₱ 45,247,939.39

Local Taxes ₱ 9,049,587.88
Insurance ₱ 4,524,793.94
License Fee/Royalty Fees ₱ 4,524,793.94
TOTAL FIXED COST ₱ 112,937,554.53

VARIABLE COSTS

Miscellaneous Operating Materials (MOM)

Miscellaneous Operating Materials = (Maintenance Cost) (0.10)

Miscellaneous Operating Materials = ₱ 45,247,939.39 (0.10)

MOM: ₱ 4,524,793.94

RAW MATERIAL COST:

Table 6.45: Raw Material for Direct Synthesis of Adipic Acid

Raw Material Cost (PHP/10 MT)

Cyclohexene ₱ 1,286,899.00
Acetic Acid ₱ 1,526,799.00
HMDA ₱ 258,057.00
Hydrogen Peroxide ₱ 580,338.00
TOTAL: ₱ 3,652,093.00

Table 6.46: Summary of Variable Cost for Direct Synthesis of Adipic Acid

VARIABLE COSTS
Miscellaneous Operating Materials ₱ 4,524,793.94
Raw Materials Cost ₱ 3,652,093.00
TOTAL VARIABLE COST ₱ 8,176,886.94

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Direct Production Cost = VC + TFC

Direct Production Cost = ₱ 8,176,886.94 + ₱ 112,937,554.53

DPC = ₱ 121,548,691.47

OTHER COSTS

Sales Expense (SE)

Sales Expense = Direct Production Cost (0.20)

Sales Expense = ₱ 121,548,691.47 (0.20)

SE = ₱ 24,309,738.29

General Overheads (GO)

General Overheads = (DPC) (0.25)

General Overheads = ₱ 121,548,691.47 (0.25)

GO: ₱ 30,387,172.87

Research and Development (R&D)

Research and Development = (DPC) (0.28)

Research and Development = ₱ 121,548,691.47 (0.28)

R&D = ₱ 34,033,633.61

Table 6.47: Summary of Other Costs for direct synthesis of adipic acid

OTHER COSTS
 
SE ₱ 24,309,738.29
GO ₱ 30,387,172.87
R&D ₱ 34,033,633.61
TOTAL OTHER COST ₱ 88,730,544.77

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Annual Production Cost = DPC + OC

Annual Production Cost = ₱ 121,548,691.47 + ₱ 88,413,542.27

APC = ₱ 210,279,236.25

PRODUCTION COST:

Annual Production Cost

Production Cost = Plant capacity days
( day )
(300 working
year
)

₱ 210,279,236.25
Production Cost = 200 MT days
( )(300 working )
day year

Production Cost = ₱ 3,504.65

VIII. MANUFACTURABILITY

PURITY

The Polyhexamethylene Adipamide obtain from the Multi-stage

Distillation Column Reactor Process has a purity of 98%. (29.
10.3303/CET1229095.)

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YIELD

The Polyhexamethylene Adipamide obtain from the Multi-stage Distillation

Column Reactor Process has a yield 73%. ((29. 10.3303/CET1229095.)

PROCESS USAGE

The production of polyhexamethylene adipamide from direct synthesis of

adipic acid is not being used.

IX. SAFETY

Table 6.48 – Parameters for Adipic Synthesis Process

PARAMETERS RANGE
Temperature 260 ºC

Pressure 1 atm

TOXILOGICAL RATING

The toxicity of raw materials is examined based on the health hazards

level that can harm people. The health hazards of the raw material are based
from the Material Safety Data Sheet and the table below was used to evaluate
the toxicity level.

Table 6.49: Health Hazard Rating from Direct Synthesis of Adipic Acid

HEALTH HAZARD RATING

0 For minimal hazard and no significant risk to health

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1 For slight hazard or minor reversible injury possible

2 For moderate hazard, temporary or minor injury may occur

3 For serious hazard, major injury likely unless prompt action is taken,
medical treatment given

4 For severe hazard, life-threatening, major of permanent damage may

result from single or repeated exposures

Table 6.50: Toxicity Level Scores of Raw Materials and Products from Direct Synthesis
of Adipic Acid

Criteria Weigh Major Raw Materials Product

t

Cyclohexen Aceti Hexamethylen Hydroge Nylon 6,6

e c e Diamine n
Acid Peroxide

Severity of 0.1 3 2 4 3 0
Immediate
Effects
Sensitization 0.1 3 2 4 3 1
Level

Carcinogenicit 0.3 0 0 0 0 1
y Level

Reproduce 0.25 1 1 3 1 0
Toxicity Level

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Severity of 0.25 4 2 4 2 0
Chronic
Effects
Weighted 1.85 1.15 2.55 1.35 1
Score

Average 1.51
Weighted
Score

Table 6.51: Basis of Toxicity Level Scores for Raw Materials from Direct Synthesis of
Adipic Acid

Criteria Raw Materials

Cyclohexene Acetic Acid Hexamethylene Hydrogen

Diamine Peroxide

Severity of May cause May cause May cause eye May cause
Immediate eye eye irritation irritation, skin eye
Effects irritation and skin damage and irritation,
and skin damage difficulty in skin damage
damage breathing and
difficulty in
breathing
Sensitization Irritant Irritant Irritant Irritant
Level

Carcinogenicit Not listed Not listed as Not listed as Not listed as

y Level as carcinogen carcinogen carcinogen
carcinoge
n
Reproduce Mutagenic Non- Mutagenic Non-
Toxicity Level mutagenic mutagenic

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Severity of High Prolonged eye Prolonged eye Prolonged

Chronic Effects exposure and skin and skin contact eye and skin
may cause contact may may cause contact may
tremors, cause severe severe eye and cause severe
collapse eye damage skin damage eye and skin
and coma. and shortness and difficulty in damage.
of breath. breathing.

Table 6.52: Basis of Toxicity Level Scores for Product from direct synthesis of adipic
acid

Criteria Product

Nylon 6,6

Severity of Immediate May not cause skin, eye and lung

Effects damage

Sensitization Level Irritant

Carcinogenicity Level Carcinogenic in some aspects

Reproduce Toxicity Non-mutagenic

Level

Severity of Chronic May cause severe itchiness as

Effects textile.

X. ENVIRONMENTAL IMPACT

The basis for the environmental hazard for the Production of

Polyhexamethylene Adipamide From Direct Synthesis of Adipic Acid Process is
the raw materials and product. The environmental hazard data is based on the
harmful effects of the materials to the environment and the table below was used
to evaluate the toxicity level.

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Table 6.53: Environmental Hazard Rating

ENVIRONMENTAL HAZARD RATING

0 For minimal hazard and no significant risk to the environment

1 For slight hazard or minor reversible damage possible

2 For moderate hazard, temporary or minor damage may occur

3 For serious hazard, major damage to environment unless prompt action

is taken

4 For severe hazard, permanent damage may result

Table 6.54: Environmental Hazard Level Scores of Raw Materials and Products

Produ
Major Raw Materials
ct
Criteria Weight
Cyclohexene
Acetic
HMDA H 2 O 2 Nylon
Acid 6,6

Aquatic
0.2 3 1 2 0 0
Toxicity

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Toxicity on
Plants and 0.25 2 1 3 0 0
Animals
Toxicity of
Immediate 0.2 1 0 0 1 0
Degradation
Long-term
Degradation 0.35 1 0 1 1 1
Effect
Weighted  
1.65 0.45 1.5 2 0.35
Score
Average  
Weighted 1.19
Score

Table 6.55: Basis of Environmental Hazard Level Scores for Raw Materials

Criteria Raw Materials

Cyclohexene Acetic Hexamethylene Hydrogen

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Acid Diamine Peroxide

Aquatic Dangerous to No Dangerous to No known

Toxicity Aquatic Life known Aquatic Life toxic
toxic effects
effects
Toxicity on Dangerous for No Dangerous for No known
Plants and plants and known plants and toxic
Animals animals toxic animals effects
effects
Toxicity of No known toxic No No known toxic No known
Immediate effects known effects toxic
Degradation toxic effects
effects
Long-term No known toxic No No known toxic No known
Degradation effects known effects toxic
Effect toxic effects
effects

Table 6.56: Basis of Environmental Hazard Level Scores for Products

Criteria Product

Nylon 6,6

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Aquatic Toxicity No known toxic effects

Toxicity on Plants and Animals No known toxic effects

Toxicity of Immediate Degradation No known toxic effects

Long-term Degradation Effect No known toxic effects

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SUMMARY OF
PROCESS
SELECTION

SUMMARY OF EVALUATION OF THE THREE PROCESSES FOR THE

PRODUCTION OF POLYHEXAMETHYLENE ADIPAMIDE

The table below summarize the best choice among the three processes since
selection is a very important step in selecting the right process.

Table 6.57 Summary of Process Selection

CRITERIA PROCESS 1 PROCESS 2 PROCESS 3

Step-growth Multistage Synthesis of

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Polymerization Distillation Adipic Acid

Process Column Reactor
Process
PLANT ECONOMY

Raw Material The raw materials The raw materials The raw materials
Cost for this process are for this process for this process are
The raw material is Hexamethylene are Ammonia, Cyclohexene,
estimated for every Diamine, Adipic Acid, Acetic Acid,
10 MT.
Cyclohexane, Hexamethylene Hexamethylene
Water and Nitric Diamine and Diamine and
Acid. The cost is water. The cost is Hydrogen Peroxide.
estimated at 10 MT estimated at 10 The total raw
of raw material. MT of raw material cost is
The total raw material. The ₱ 3,652,093.00
material cost is total raw material
₱ 2,398,614.70 cost is
₱2,589,693.00

Total Capital The process has a The process has a The process has a
Investment total of 37 total of 14 total of 26
equipment. The equipment. The equipment. The
total capital total capital total capital
investment is investment is investment is
₱573,838,361.33 ₱471,096,674.53 ₱563,155,090.00

Annual The raw materials The raw materials The raw materials
Production are Hexamethylene for this process for this process are
Cost Diamine, are Ammonia, Cyclohexene,
The annual Cyclohexane, Adipic Acid, Acetic Acid,
production cost is Water and Nitric Hexamethylene Hexamethylene
dependent on the
raw materials cost.
Acid. The annual Diamine and Diamine and
production cost is water. The annual Hydrogen Peroxide.
₱248,028,882.03 production cost is The annual
₱206,039,657.45 Production cost is
₱209,527,983.75

ENERGY REQUIREMENT

Operating The poly reactor The multistage The autoclave has

Temperature has an operating distillation an operating
The energy temperature of 400 column reactor temperature of
requirement is °C has an operating 260°C
based on the

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temperature of the temperature of

reactors. 280 °C

MANUFACTURABILITY

No. of Intensive The number of The number of The number of

Equipment intensive intensive intensive equipment
The number of equipment for the equipment for the for the third process
intensive equipment first process is 4. second process is is 2.
is based on the
equipment that
2.
requires a certain
amount of pressure.
Process Usage The process is This process is This process is not
only proposed by yet used by any
being used by the
Du Pont de manufacturing
four manufacturing Nemours and Co. plants.
plants namely as
Allied Chemical,
Celanese
Corporation, Du
Pont Orange, Du
Pont Victoria and
Monsanto.

SUSTAINABILITY

Availability of The raw materials The raw materials The raw materials
Raw Materials for this process are for this process for this process are
The availability of all locally available are all locally all locally available
Raw Materials is and the total available and the and the total
based on their
proximity is 120 total proximity is proximity is 110
proximity.
km. 130 km. km.
SAFETY

Toxicity Level The raw materials All the raw The raw materials
of Raw are not listed as materials are are all irritant and
Materials carcinogenic but irritant and can can cause chronic
the product can be cause chronic effects but none is
considered if there effects and only listed as
is formation of the ammonia and carcinogenic bull

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formaldehyde. All HMDA are all the raw

the raw materials mutagenic. This materials are
are irritant and the process has a mutagenic. This
HMDA mutagenic. toxicity rating of process has a
This process has a 1.66 toxicity rating of
toxicity rating of 1.51
1.32
ENVIRONMENTAL HAZARDS

Environmental All the raw Raw material The raw materials

Impact materials are toxic such as Ammonia for this process are
for plants and at high all toxic for plants
animals in different concentration and and animals at high
level. The process HMDA is both concentration
has an toxic for plants except for the
environmental and animals. The hydrogen peroxide.
rating of 1.32 process has an The process has an
environmental environmental
rating of 1.28 rating of 1.19

Table 6.58 Quantitative Summary of the Criteria for Process Selection

CRITERIA PROCESS 1 PROCESS 2 PROCESS 3

Step-growth Multistage Synthesis of Adipic
Polymerization Distillation Acid
Process Column
Reactor Process
PLANT ECONOMY

Raw Material ₱ 2,398,614.70 ₱2,589,693.00 ₱ 3,652,093.00

Cost
Total Capital ₱573,838,361.33 ₱471,096,674.53 ₱563,155,090.00
Investment
Annual ₱248,028,882.03 ₱206,039,657.45 ₱209,527,983.75
Production
Cost
ENERGY REQUIREMENT

Operating 350.00 °C 400.00 °C 280°C

Temperature
MANUFACTURABILITY

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No. of Intensive 4 2 2
Equipment
Process Usage 4 1 1

SUSTAINABILITY

Availability of 120 130 110

Raw Materials
SAFETY

Toxicity Level 1.32 1.66 1.51

of Raw
Materials
ENVIRONMENTAL HAZARDS

Environmental 1.25 1.28 1.19

Impact

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Table 6.59 Normalized Scores of the Three Processes

CRITERIA PROCESS 1 PROCESS 2 PROCESS 3

Step-growth Multistage Synthesis of Adipic
Polymerization Distillation Acid
Process Column
Reactor Process
PLANT ECONOMY

Raw Material 3.00 2.843 1.970

Cost
Total Capital 2.463 3.00 2.519
Investment
Annual 2.492 3.00 2.958
Production
Cost
ENERGY REQUIREMENT

Operating 1.950 2.850 3.00

Temperature
MANUFACTURABILITY

No. of Intensive 3.00 1.50 1.50

Equipment
Process Usage 3.00 0.00 0.00

SUSTAINABILITY

Availability of 2.769 2.538 3.00

Raw Materials
SAFETY

Toxicity Level 3.00 2.376 2.651

of Raw
Materials
ENVIRONMENTAL HAZARDS

Environmental 2.705 2.795 3.00

Impact
Basis of scoring: 0-3, 3 being the highest

SCORING

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The scores obtained from the attributes will determine the optimum process. The
transmuted score is obtained by multiplying the given weight of each the
attribute with the normalize score and the highest score is 3.

Table 6.60 Summary of Scores of the Three Processes

Attributes Normalized Transmuted Scores

Scores
P1 P2 P3 P1 P2 P3
Weight
1 Raw Materials 0.22 3.00 2.84 1.97 0.660 0.625 0.433
Cost

2 Total Capital 0.23 2.47 3.00 2.52 0.566 0.69 0.579

ECONOMY Investment
3 Annual 0.21 2.49 3.00 2.96 0.523 0.630 0.621
Production
Cost
1 Operating 0.04 1.95 2.85 3.00 0.078 0.114 0.12
Temp.
1 [Link]
ENERGY of 0.03 3.00 1.5 1.5 0.09 0.045 0.045
intensive
Equipment

MANUFACTURABILITY
2 Process Usage 0.06 3.00 0.00 0.00 0.18 0.00 0.00

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1 Availability of 0.08 2.77 2.54 3.00 0.222 0.203 0.240

Raw Materials

SUSTAINABILITY

1 Toxicological 0.06 3.00 2.38 2.65 0.180 0.143 0.159

Rating
SAFETY

1 Environmental 0.07 2.71 2.80 3.00 0.189 0.196 0.210

Hazards

ENVIRONMENTAL IMPACT

TOTAL: 1.00 2.689 2.646 2.408

Basis of Scoring: 3 being the highest.

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Evaluation of the Processes

The attributes that have been considered for this process selection played
an important role as well as the cost of equipment since it affects the
determination of the optimum process. The results have comparable values that
differentiate the three processes. These attributes are the Raw Materials Cost,
Total Capital Investment, Annual Production Cost, Energy Requirement,
Number of Intensive Equipment, Process Usage, Availability of Raw Materials,
Toxicological Rating and Environmental Impact. Each value of the attributes has
given a weight that depends on their importance. The first process which is the
Production of the Polyhexamethylene Adipamide (Nylon 6,6) via
Polycondensation and Step-growth Polymerization attained the highest score of
2.689, therefore this chosen process is the most feasible among the other
processes for the production of Nylon 6,6.

In the evaluated score, the second process which is via multistage

distillation column reactor obtained the highest score for the two attributes
which are the total capital investment and annual production cost and the third
process which is the synthesis of adipic acid obtained the highest score for
environmental impact. However, the chosen process obtained the highest score
for the cost of raw materials, process usage since many manufacturing plants are
using this process, and the safety of the materials. The two process are only
experimental and has not been used by any manufacturing plants. All the
manufacturing plants that produce nylon 6,6 used the polycondensation and step-

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growth polymerization therefore the first process is the most feasible among the
three processes.

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