PROPYLENE AND ETHYLENE

PRODUCTION FROM
METHANOL

Group Members:
Czarina Kasmally
Andrea Lal
Rachel Kalliecharan
Jillian Estwick
 Table of Contents

Contents
1.0 Executive Summary ............................................................................. 6

2.0 Introduction .......................................................................................... 7

3.0 Scope .................................................................................................... 9

3.1 Limitations ..................................................................................................................... 10
3.2 Deliverables .................................................................................................................... 10
4.0 Gantt Chart ......................................................................................... 12

5.0 Process Description............................................................................ 15

5.1 SWOT Analysis on the Production of Propylene and Ethylene (Jillian) ....................... 15
5.2 MTO process converts methanol to olefins.................................................................... 15
5.3 Methanol to propylene Process. ..................................................................................... 17
5.4 Process selection ............................................................................................................ 19
5.5 Selected Process Description ......................................................................................... 20
5.6 Methanol to Olefins (MTO) Process Block Flow Diagram (Jillian).............................. 23
6.0 Market Summary ............................................................................... 24
6.1 Propylene Market Survey ............................................................................................... 24
6.2 Ethylene Market Survey ................................................................................................. 28
6.3 Methanol Market Survey................................................................................................ 32
7.0 Mass and Energy Balances ................................................................ 35
7.1 Reactor Mass and Energy Balance ...................................................................................... 35
7.2 Absorption Column Mass and Energy Balance ............................................................. 37
7.3 De-Propanizer Column Mass and Energy Balance ............................................................. 37
7.4 De-Methanizer Column Mass and Energy Balance ....................................................... 39
8.0 Equipment Design Calculations ........................................................ 41
 8.1 Reactor Design calculations ........................................................................................... 41
8.2 Absorption Column Design Calculations ....................................................................... 47
8.3 De-Propanizer Column Design Calculations and Sensitivity ........................................ 49
8.4 De-Methanizer Column Design Calculations and Sensitivity ....................................... 57
8.5 Heat Exchanger Design Calculations ............................................................................. 63
9.0 Process Simulations ........................................................................... 64

10.0 Financial Operating Model and Selectivity Analysis .................. 71

11.0 Overall Control Strategy .............................................................. 73

12.0 P&ID’s.......................................................................................... 81

13.0 HAZOP ......................................................................................... 85

13.1 HAZOP Analysis of Methanol to Olefins (MTO) Reactor ............................................ 85
13.2 HAZOP performed on Absorber unit (czarina)............................................................. 95
13.3 HAZOP Performed on the De-Propanizer Column........................................................ 97
13.4 Hazop on De-Methanizer Column ............................................................................... 105
14.0 HEALTH, SAFETY AND ENVIRONMENT (HSE) ............... 113

15.0 Site plan ........................................................................................ 12

16.0 References .................................................................................... 16

Table of figures:

Figure 1-MTO process to desired products (Ethylene and Propylene) Using Natural Gas ............ 8
Figure 2- Gantt Chart .................................................................................................................... 12
Figure 3- Gantt Chart .................................................................................................................... 13
Figure 4- Gantt Chart .................................................................................................................... 14
Figure 5- Propylene and its derivable products ............................................................................ 24
Figure 6- Propylene pricing from 2005 to 2020 in US dollars per ton ......................................... 25
Figure 7-Pie chart shows the product demand for propylene ....................................................... 25
Figure 8- Propylene market forecast and its products .................................................................. 27
Figure 9- Showing the sources of ethylene in 2016 ...................................................................... 28
Figure 10- Showing the uses of ethylene in 2016 ......................................................................... 28
Figure 11- Showing the worldwide usage/consumption of ethylene in 2016 ............................... 29
Figure 12- Showing the global ethylene demand ......................................................................... 30
Figure 13- Showing the global cash cost of ethylene in 2016 ...................................................... 31
Figure 14- Showing Uses of Methanol ......................................................................................... 32
Figure 15- Global Demand of Methanol for 2000-2016 and Projections for 2017- 2020 ............ 33
Figure 16- Methanol Demand by End Application....................................................................... 34
Figure 17- Sensitivtiy Analysis of Column Diameter .................................................................. 49
Figure 18-Showing the relationship between reflux ratio and the height and diameter of the
column........................................................................................................................................... 55
Figure 19- Showing the relationship between reflux ratio and the cost of the column ................ 56
Figure 20- Showing the relationship between reflux ratio and the duty of the condenser ........... 56
Figure 21- Graph of Column Diameter and height vs. Reflux ratio ............................................. 61
Figure 22- Costing vs. Reflux Ratio ............................................................................................. 62
Figure 23- Hysys Simulation ........................................................................................................ 65
Figure 24- Hysys Rigorous Plant .................................................................................................. 65
Figure 25- Site Plan ...................................................................................................................... 13

Table 1- SWOT Analysis .............................................................................................................. 17

Table 2- SWOT Evaluation .......................................................................................................... 20
Table 3- De- Propanizer Mass Balance ........................................................................................ 37
Table 4- Flow Rates ...................................................................................................................... 40
Table 5- Mole fraction and Molar flows ....................................................................................... 40
Table 6- Heat Needed for Equipment ........................................................................................... 40
Table 7-Heat needed for reboilers................................................................................................. 40
Table 8- Calculated Height Reactor .............................................................................................. 43
Table 9- Sensitivity Data for Reactor ........................................................................................... 45
Table 10- values for the provisional plate design: ........................................................................ 52
Table 11- values for the total plate pressure drop calculation ...................................................... 53
Table 12- De-Propanizer Sensitvity .............................................................................................. 54
Table 13- Rmin Values ................................................................................................................. 57
Table 14- surface tension and Average molecular mass ............................................................... 59
Table 15- Hydraulic Plate Design ................................................................................................. 59
Table 16- Calculating Column Diameter ...................................................................................... 59
Table 17- provisional plate design ................................................................................................ 60
Table 18- pressure drop values ..................................................................................................... 60
Table 19- data of height, diameter and reflux ratio. ..................................................................... 61
Table 20- Reflux ratio and Cost. ................................................................................................... 62
Table 21- Hysys Evaluation of Reactor ........................................................................................ 66
Table 22- Hysys SImulation of De- Propanizer Column .............................................................. 67
 Executive Summary
(Jillian)
This project focuses on designing a production plant which produces approximately 6000 tons of
Propylene (C3H6) and Ethylene (C2H4) per year. In recent years there has been new technology
developed for the production of these compounds from a non-oil resources, such as natural gas
and methanol. Our design is based on the production of these olefins while utilizing methanol
as raw material. Since Trinidad and Tobago has methanol locally available and in no short
supply, and with the current situation of our oil reserves, diversification is needed to assist in the
generating of new revenue streams for our country. From the initial mass balance, approximately
0.21kg/sec of C3H6 is required to meet the set target goal. The purity of Ethylene (C2H4)
produced is 92% and 95% Propylene (C3H6).

These compounds produced can be sold locally both to the chemical and petrochemical
industry. Propylene and ethylene can be produced from numerous processes, however the two
main processes that utilizes methanol as a feed stock is the methanol to olefins (MTO) process
and the methanol to propylene (MTP) process. The MTO process was selected based on the
SWOT analysis done, receiving an overall score of 68 out of 100 compared to the MTP process
which scored 54. The parameters with the heavier weighting were the availability of design data
and the ability to produce C2H4 as well as C3H6 as a product, having the MTO
process earned high scores in these areas is what allowed for the process to be selected.

After doing a concise market research, trends were seen where the demand for propylene would
continue to rise to approximately 130 million Tpy, by the year 2024 mainly due to the production
of polypropylene which is primarily used to make plastics for the packaging
industry. The ethylene market is also expected to increase worldwide at a CAGR
(compound annual growth rate) of about 11.26% between the years 2016 to 2025. This is due
to necessities such as packaging and construction materials.

The major equipment designed for the MTO plant model are:
 1 Fluidizing bed Reactor
 1 Absorber
  4 distillation columns.

The minor equipment designed for the MTO plant model are:
 Heat Exchangers
 Reboilers
 Condensers

This design project incorporates mass and energy balances, sizing of the respective equipment,
followed by modelling of all major equipment on hysys, costing of both major and minor
equipment and a financial feasibility analysis to provide insight on the economics of the plant.
Based on the financial feasibility analysis the plant was seen to be operating at a loss and
therefore was not feasible. The health and safety aspect of the proposed plant was also covered
within the report, along with recommendations and mitigations for handling and storing of the
produced compounds.

Introduction
(Rachel)
Worldwide in the chemical and petrochemical industries, high-value products such as ethylene and
propylene were traditionally produced from crude oil. However, the downside to this is that the
price of crude oil is very high, costing almost six times the price it was in early 1999. As a result,
an advanced methanol to olefins (MTO) process was developed and commercialized in 2009 as an
innovative technology to provide a pathway to produce ethylene and propylene from methanol.

Producing these high-value products from methanol is advantageous since methanol can be
produced from many different types of feedstock. Therefore, this MTO process provides an
alternative pathway to produce the desired products starting from cost effective raw materials such
as natural gas which is significantly cheaper than the price of oil for the same energy content (refer
to Figure 1.0).

Figure 1-MTO process to desired products (Ethylene and Propylene) Using Natural Gas

The MTO process has been widely studied dated back to the 1970s and early 1980s where
methanol was initially converted to gasoline range products, utilizing ZSM-5 type zeolites.
Unfortunately, the selectivity of the methanol to ethylene and propylene using these zeolite types
was very low, favoring heavier, more highly branched hydrocarbons and aromatics. In the 1980s
a specific group of scientists at Union Carbide had a breakthrough in their research and analyses
when they discovered a new class of materials referred to as silicoaluminumphosphates (SAPO)
molecular sieves.

Of these, the SAPO-34 seemed the most plausible and led to a technological breakthrough. It was
the SAPO-34’s unique pore size, geometry and acidity which provided a more selective route for
the methanol conversion to make the desired products ethylene and propylene but with reduced
heavy byproducts. Owing to the smaller pore size of the SAPO-34, the diffusion of the heavier and
branched hydrocarbons was restricted and the high selectivity of the desired light olefins was
achieved. This therefore solved the problem that was first seen with the ZSM-5 type zeolites.

There are four licensed MTO units in China which utilizes either purchased methanol or coal. As
of 2015, approximately more than 10 million tpy (tons per year) of combined ethylene plus
propylene was produced from MTO technologies.

Ethylene and propylene are the backbone of petrochemical processes given their high double bond
reactivity, making light olefin ideal molecules for being converted into many useful end products.

Ethylene is used to produce:

1. Polyethylene used in food packaging,

2. Polyvinylchloride used in construction materials and
3. Polystyrene used for insulation.

Similarly, propylene is used to produce:

1. Polypropylene which can be used in the manufacture of films, packaging and automotive
components.
2. Acrylonitrile used in synthetic rubbers
3. Propylene oxide used in antifreeze, polyurethane foams

Some of the major factors which are responsible for shaping the development of petrochemical
markets include regional demand as well as availability and cost of key raw materials. Therefore,
by using the MTO process, new production pathways for the desired products were achieved that
utilized lower costs as well as alternative, more readily available feedstock.

Scope
(Rachel)

To design a plant which utilizes the Methanol to Olefins (MTO) process in an effort to produce
ethylene and propylene while using methanol as the feedstock. In terms of production, the target
goal is set as being six thousand tons of propylene per year.
 Limitations
Due to time constraints, the full design calculations were not performed on all the
equipment.
Pertinent data was not found for the amine solution designed for the removal of 99.9% of
CO2 in the Absorption Column and an alternate amine solution was used instead which did
not achieve that desired removal of CO2. This may have affected the assumption made that
there was negligible to no CO2 entering the downstream unit operations.
The Methanol to Olefins Process is a relatively new process that requires advanced
technology which can be very expensive and not easily accessible

Deliverables
The process for achieving the desired products (ethylene and propylene) from methanol was
extensively researched and a suitable process with sufficient information was selected as being the
Methanol to Olefins (MTO) Process. After becoming familiarized or acquainted with the process
that was chosen, process descriptions pertaining to each specific unit operation were strategically
and carefully outlined.

A market survey was conducted to attain the demand, supply, uses, prices and sources of the
ethylene market. The market survey was seen as an important tool to gathering data on the target
market (ethylene, propylene and methanol) such as pricing trends, customer requirements,
competitor analysis and other such details in order to make well-informed business decisions,
receive critical feedback and even enhance the desired final products.

Mass and energy balances and full design calculations were to be done by each group member
pertaining to their assigned unit operation. This allowed the students to apply their previously
acquired theoretical and experimental knowledge and skills and design a significant process
engineering system to meet specific needs.

Also, the group members were assigned their own specific Health, Safety and Environment (HSE)
sections which included: finding information such as the chemical toxicity and proper Personal
Protective Equipment (PPE) when handling the components involved in the process; the various
forms of pollution that the process is susceptible to and; the HSE for the assigned respective unit
operations.
REFERENCES

(2019). Retrieved from https://www.uop.com/wp-content/uploads/2013/12/Methanol-to-Olefins-

Technology_Hydrocarbon-Engineering-Dec-2013.pdf
 Gantt Chart
Gantt Chart (Andrea)

Figure 2- Gantt Chart

Figure 3- Gantt Chart
Figure 4- Gantt Chart
 Process Description

5.1 SWOT Analysis on the Production of Propylene and Ethylene (Jillian)

Propylene and ethylene are the two most important olefins used within the petrochemical and
chemical industry. They are the building blocks from which countless things are produced and
utilized within our daily life, thereby creating an ever-growing demand of these compounds. In
recent years new technology of obtaining these olefins from nonoil resources natural gas, coal
and methanol has attracted considerable attention. This new technology offers a way to
manufacture lower olefins with high yield and selectivity, with the fraction of ethylene and, or
propylene in the hydrocarbon product being above 80mol %. A SWOT analysis was therefore
performed on two possible processes, methanol-to-olefins (MTO) and methanol-to- propylene
(MTP) and documented below.

5.2 MTO process converts methanol to olefins.

This process consists of two main sections, methanol to olefin reaction and product purification
and separation. Firstly, methanol is converted to dimethyl ether (DME) and water:

2CH3OH → CH3OCH3 + H2O

Next, DME is converted to both ethylene and propylene. The ratio between ethylene and
propylene production depends on the catalyst, reaction parameters and the technology, and is
done in the presence of a SAPO-34-type zeolite catalyst.

CH3OCH3 → C2H4 + H2O

3CH3OCH3 → 2C3H6 + 3H2O

 STRENGTHS WEAKNESSES

1. Process converts crude methanol to

olefins. 1. Process requires selective catalyst that
2. Uniform bed temperature. operates at moderate to high
3. Continuous regeneration of the temperatures.
catalyst (constant catalyst activity) 2. Due to the use of a fluidized bed
4. Both ethylene and propylene are reactor scale-up of the process can be
produced with this process. difficult.
5. Utilizes a fluidized bed reactor which 3. Higher fixed capital investment cost.
provides excellent heat transfer
properties.
6. Process is more straight-ward, with
more design data available.

OPPORTUNITIES THREATS

1. A chance to produce basic 1. The reactor regeneration system

petrochemicals from nonoil resources carry’s a high risk for explosion.
such as coal and natural gas. 2. In the USA shale gas is rapidly
2. MTO provides an opportunity for becoming an alternative fuel source
Trinidad and Tobago to compete in which can be used to affordably
the global market, by the exportation produce methanol. Therefore, their
of products manufactured from the ability to compete in the global market
ethylene and propylene. This can be within the petrochemical industry at
achieved by building petrochemical lower production cost can create major
plants which utilizes ethylene as a issues for their competitors and
feed stock to manufacture plastics, smaller countries such as Trinidad and
films, detergents, synthetic lubricants, Tobago.
and styrenes (used to make protective
packaging). And plants which utilizes
propylene to make polypropylene, a
 versatile plastic polymer used to make
products ranging from carpets to
structural foam.

5.3 Methanol to propylene Process.

The Lurgi Methanol-to-propylene (MTP) process converts methanol to propylene. Purified

methanol is sent to the first reactor, the DME reactor, where methanol is converted to DME and
water.

2CH3OH → CH3OCH3 + H2O

This stream is then routed to the reaction section where the olefin reaction takes place in a fixed
bed reactor, in the presence of a zeolite-based catalyst (ZSM-5). To maintain the process
conditions over the reactor, five or six catalyst beds are utilized. The product stream is then
directed to the separation section where water is removed and rerouted to the reaction section.
After product conditioning, the product stream is sent to a fractionator. There, the product stream
is split up into the desired products, such as propylene and gasoline as well LPG and fuel gas. A
stream of medium boiling hydrocarbons is rerouted from fractionation to the reaction section to
improve the yield of propylene.

Table 1- SWOT Analysis

STRENGTHS WEAKNESSES

1. A fixed bed reactor is used for this 1. Crude methanol must be purified prior
process which has lower investment to the reaction; hence an additional
costs. distillation column is needed.
2. The fixed bed reactor is easier to scale 2. Temperature control of the methanol
up, provides higher product selectivity conversion within the fixed bed
 and has very limited by-product reactor is not as straightforward as in
formation. fluidized bed reactors.
3. Uniform residence times for reactants. 3. Catalytic bed must be put out of
service to remove the built-up coke.
4. MTP produces mainly propylene and
only small amounts of gasoline. No
ethylene is produced from this
process.
5. Low to moderate heat transfer
properties due to the fixed bed reactor.
6. Process is more complex, with design
data not readily available.
OPPORTUNITIES THREATS

1. A chance to produce basic 1. In the USA shale gas is rapidly

petrochemicals from nonoil resources becoming an alternative fuel source
such as coal and natural gas. which can be used to affordably
produce methanol. Therefore, their
2. MTP provides an opportunity for
ability to compete in the global market
Trinidad and Tobago to compete in
within the petrochemical industry at
the global market, by the exportation
lower production cost can create major
of products manufactured from the
issues for their competitors and
propylene. This can be achieved by
smaller countries such as Trinidad and
building petrochemical plants which
Tobago.
utilizes propylene to
make polypropylene, a versatile
plastic polymer used to make products
ranging from carpets to structural
foam.
 5.4 Process selection

The parameters and their assigned percentages were chosen because of the following reasons:

1. Ability to use crude methanol as feed stock (5%): If crude methanol is to be purified
prior to entering the reactor, then a purification system would need to be purchased and
installed upstream the reactor which would be an additional cost.

2. Ethylene produced as a product. (20%): This was given a heavy weighting since the
production of ethylene was one of the main objectives outlined within the scope of the
project.

3. Continuous regeneration of catalyst on the run. (10%): This system is more efficient for
continuous production and reduces unnecessary downtime.

4. Scale-up of process (10%): Commercialization of the selected process is essential,

however because of the difference in the reactor types between the both processes, large
scale production may not be easily obtained.

5. Fixed Capital Investment (15 %): Because of the variations between both processes,
different equipment is utilized, resulting in a difference in costing.

6. Complexity of the process (15%): With the different equipment utilized by the various
processes, some reaction pathways were found to be easily understood, while others were
found to be more difficult.

7. Availability of design data (25 %): A large weighting was given to this parameter, since
the successful completion of this project depends on the availability of data for
calculations and equipment design.
Table 1: Shows an evaluation of both processes and their suitability for the production of
Propylene and Ethylene from methanol.

Table 2- SWOT Evaluation

Methanol-to-Olefins Methanol-to-Propylene
Parameters
(MTO) (MTP)
Ability to use crude methanol as feed
5 1
stock. (5%)
Ethylene produced as a product.
4 1
(20%)
Continuous regeneration of catalyst
5 1
on the run. (10%)

Scale-up of process (10%) 2 5

Fixed Capital Investment (15 %) 3 5

Complexity of the process (15%) 3 4

Availability of design data (25 %) 3 2

Total Scores 68 54

Note: Each parameter was evaluated using a rating of 1 to 5, with 5 being the highest. The total
overall rating was then calculated.

5.5 Selected Process Description

As determined from our SWOT analysis, the process found to be most appropriate to produce
both propylene and ethylene, was Methanol-to-Olefins (MTO). This process when evaluated
against the specified parameters scored the highest overall rating. (Jillian)

The MTO technology is based on the dehydration of MeOH to light olefins in a catalytic reactor.
A diluted methanol (MeOH) stream, consisting of 50 mole% MeOH and 50 mole% water (H2O)
is feed into a fluidizing bed reactor at a temperature of 400-degree C and 40 bars, in the presence
of an H-SAP0-34 zeolite type catalyst. The product stream comprising of methane, ethane,
ethylene, propane, propylene, butane, pentene, carbon-dioxide and water is then cooled to 40°C
and flashed to remove the water present within the product stream of the MTO reactor. (Jillian)

Upon exiting the flash tank, the product is further cooled to 25 ℃ before entering the bottom of
the absorber. This process utilizes diglycolamine (DGA) but was substituted for a 17%
monoethanolamine (MEA) solution due to the unavailability of equilibrium data for DGA.
(Czarina)

The Column operates at 25 ℃ and 1 atm and is randomly packed with 50 mm Pall Rings. As the
gas enters the Column is flows upwards through the column in counter-current contact of lean
aqueous MEA. A chemical reaction occurs whereby the amine solution absorbs the CO2 from the
gas. The gas product exiting at the top of the Column, now free of CO2 is heated to 37℃ and
sent to the De-Ethanizer. The absorber is designed to remove 90% of CO2 and any remaining
CO2 is assumed negligible for this design. The rich MEA exits at the bottom of the Column and
is sent to the stripping section for regeneration. (Czarina)

The tops product stream from the CO2 Absorber column containing the olefins (methane;
ethylene; ethane; propylene; propane; butene; pentene) and a trace amount of carbon dioxide, is
compressed to 35 bars where it is assumed that negligible CO2 enters the downstream unit
operations. This stream is then fed into the De-Ethanizer column at 37°C and the 35 bars to
separate methane, ethylene and ethane from the propylene and the heavier components to obtain
an ethane recovery of approximately 99.8% at the tops and a propylene recovery of 99.5% at the
bottoms. The De-Ethanizer has a reflux ratio of 2.5 where 23 trays are used in order to achieve
the desired separation at an efficiency of 72%. By performing an energy balance, the total
condenser and reboiler duties are –355.9kW and 280.2kW respectively. Furthermore, the total
condenser and reboiler temperatures are -9.2°C and 90°C respectively and both operate at a
pressure of 35 bar. (Rachel)

The bottoms product from the De-Ethanizer containing the propylene, propane, butene and
pentene are sent to the De-Propanizer column at 1 bar and 90.4°C where propane is separated
from the heavier hydrocarbons, to obtain a propane recovery of 75% where the propane at the
top is taken as an impurity in the distillate stream and a butene recovery of 99.5% at the bottoms.
The De-Propanizer has a reflux ratio of 2.2 where 11 trays are used in order to achieve the
desired separation at an efficiency of 69%. By performing an energy balance, the total condenser
and reboiler duties are –300.3kW and 107.6kW respectively. Furthermore, the total condenser
and reboiler temperatures are -47.9°C and 123.8°C respectively and both operate at a pressure of
1 bar. (Rachel)

From the De-Ethanizer column’s the tops products are then sent to the De-Methanizer, where the
light gases like methane is separated from the feed. The tops products are sent into the De-
Methanizer at a pressure of 40 bars and a temperature of -9oC. The operating pressure of the
column reboiler and partial condenser is 40bars. The De-Methanizer has a reflux ratio of 0.29
and 23 trays for the separation to take place at an efficiency of 73.4%. In addition, the reboiler
operates at a temperature of 3.05oC, as the partial condenser operate at a temperature of –84.6oC.
Also, the partial condenser has a duty of 24.6kW and the reboiler duty has a duty of 78860kW.
The top production from the De-Methanizer is send to an off-gas power generation island,
whereas the bottoms product which contains mainly ethylene and ethane, is sent to a storage
vessel to be later sold. (Andrea)

Reference:

Salkuyeh, Y., & Ii, T. (2015). Co-Production of Olefins, Fuels, and Electricity from
Conventional Pipeline Gas and Shale Gas with Near-Zero CO2 Emissions. Part I: Process
Development and Technical Performance. Energies,8(5), 3739-3761. doi:10.3390/en8053739

Geankoplis, C. J. (1978). Transport Processes and Unit Operations. Boston: Allyn and Bacon.
5.6 Methanol to Olefins (MTO) Process Block Flow Diagram (Jillian)
 Market Summary

6.1 Propylene Market Survey

(Andrea)

Propylene is a colourless, flammable gas of the olefins series in organic chemistry. With the
production of propylene, there are three different grades, polymer grade of 99.5% in its purest
form, chemical grade of 93 and refinery grade of 70%. As the main difference is not within the
purities but in the price difference. Propylene mostly purchased in its polymer grade of 99.5%
due to the derivations that is obtain.

Propylene from its chemical structure is used to make a series of products such as

 Polypropylene
 Propylene oxide
 Acrylic acid
 Acrylonitrile
 Cumene
 Isopropanol
 Butanois

Figure 5- Propylene and its derivable products

 Figure 6- Propylene pricing from 2005 to 2020 in US dollars per ton
In the figure
above, we can see that the over the years the prices of propylene fluctuates, from 2005 to 2011,
and after 2011 we can see there was in increase in prices over the years that follow. We can also
predict that the price of propylene for 2020 based on market demands by North America.

Figure 7-Pie chart shows the product demand for propylene

With respect to the demand, propylene is mainly consumed in the production of polypropylene.
With polypropylene contributing to the largest volume of plastic in the world for its great
properties in density. This has spiked a demand in the production of propylene. All other
propylene products have fewer demands but are no less interesting.

Propylene-oxide takes up 7% of the demands for propylene. For its key uses are in:

 Manufacturing polyester polyols for the polyurethane industry

 Manufacturing propylene glycol

 As a component in the manufacturing of unsaturated polyester resins
In the production of acrylonitrile, made from the oxidation of propylene in the presence of
ammonia, with its key end uses are acrylonitrile-butadiene-styrene (ABS) terpolymer plastic and
acrylic fiber. It is known for its outstanding resistance concerning impact, chemical and for its
glossy appearance. This would further increase the demand for propylene.

In addition to the supply of propylene, the largest manufacture of propylene is within the
coproduction of naphtha or in liquefied petroleum gas in ethylene stream crackers. The second
largest manufactures of propylene are produces as a byproduct form fluidized catalytic cracker
(FCC). These two sources provide most of the propylene for the petrochemical industry over the
last 15 years, but as the demand for propylene grew, it’s proven to be inadequate.

According to the HIS, the demand for propylene would continue to rise to 130 million tons by
the year 2024 mainly to produce polypropylene. The demand is expected to increase by 30% in
the succeeding five-year period, not only in the US but also globally as production of the
products made from propylene increase.
 Figure 8- Propylene market forecast and its products

References:

Polypropylene price U.S. 2005-2020 | Statistic. (n.d.). Retrieved

from https://www.statista.com/statistics/796033/us-price-of-polypropylene/

The Propylene Quandary. (n.d.). Retrieved

from https://www.acs.org/content/acs/en/pressroom/cutting-edge-chemistry/the-propylene-
quandary.html
 6.2 Ethylene Market Survey
(Rachel)

Figure 9- Showing the sources of ethylene in 2016

Most regions are unable to get Ethane at a low and reasonable cost and have to use a more
expensive alternative such as Naphtha as their feedstock. It can clearly be seen that Naphtha is the
main source of ethylene in 2016, accounting for 43% of the total sources. The second most popular
source of ethylene is Ethane which accounted for 36% in 2016. The Methanol to Olefins (MTO)
process only accounts for 1% of the overall sources of ethylene. However, this MTO process
provides an alternative pathway to produce ethylene starting from cost effective feedstock like
coal or natural gas which is cheaper. The integral factors which are responsible for shaping the
development of petrochemical markets include regional demand as well as availability and cost of
key raw materials, there is a need to educate the global market on the perks associated with the
MTO process as a suitable source of ethylene.

Figure 10- Showing the uses of ethylene in 2016

Ethylene is a flammable and colorless gas which is produced in petrochemical industries which is
used extensively as a raw material in many industries such as construction and packaging. It is
used in the formation of various derivatives such as:

1. Polyethylene
2. Ethylene Oxide
3. Ethylene Dichloride (EDC)
4. Styrene
5. Alpha Olefins
6. Vinyl Acetate Monomer (VAM)

The derivatives of ethylene aforementioned are used in the manufacture of numerous chemical
products as illustrated by the pie chart shown. Some of these chemical products which are mainly
used in the packaging industries include:

1. High-density polyethylene (HDPE)

2. Low-density polyethylene (LDPE) and
3. Linear low-density polyethylene (LLDPE)

Figure 11- Showing the worldwide usage/consumption of ethylene in 2016

According to IHS Markit, Polyethylene is understood as being the ethylene derivative market
which is the most successful in terms of consumption since it accounted for approximately 62%
of the worldwide ethylene consumption in 2016. For the years 2016–21, the polyethylene market
will continue growing at an approximate rate of 4.0% annually and is estimated to remain
dominating the ethylene market in 2021, amounting to about 63%.

In 2016 IHS Markit survey, it is observed that ethylene oxide had a worldwide consumption
percentage of 15%. It is expected that this market would grow mainly in Southeast Asia and the
Indian Subcontinent at a yearly rate of 2.6% for another five years.

In 2016 IHS Markit survey, Ethylene dichloride had a global consumption of the ethylene market
which amounted to approximately 9% overall. The Ethylene dichloride market is regionally shared
between:

1. United States (31%),

2. Western Europe (19%),
3. China (9%) and
4. Japan (9%)

It is expected that this particular market would increase at a rate of approximately 2% every year.
As of 2016, the ethylene consumption should continue to rise at a yearly rate of about 3–4% for
the next five years.

Figure 12- Showing the global ethylene demand

It is expected that the ethylene market should increase worldwide at a CAGR (compound annual
growth rate) of about 11.26% between the years 2016 to 2025. This is because the ethylene demand
increases on a worldwide scale due to necessities such as packaging and construction materials.
According to the 2016 IHS Markit Survey, ethylene’s demand globally is predicted to increase
faster than the typical world GDP growth rates for a period that extends over the upcoming five
years. There are some regions which account for approximately 89% of the growth between the
years 2016 and 2021 and are, in fact, dominating the global demand of ethylene. These regions
include:

1. India (about 11% average annual growth)

2. CIS and Baltic States (about 8% average annual growth)
3. United States (about 5.8% average annual growth),
4. China (about 5.6% average annual growth), and
5. Middle East (2.5% average annual growth).

Figure 13- Showing the global cash cost of ethylene in 2016

As it can be seen, China’s methanol to olefins (MTO) process produces ethylene at the highest
cost of approximately $1200US/ton. On the other hand, the US produces ethylene at a cost of
approximately $400US/ton.

References

Ethylene. (n.d.). Retrieved from https://ihsmarkit.com/products/ethylene-chemical-economics-

handbook.html

Global Ethylene Market By End Use (Polyethylene (PE), Ethylene Oxide, Ethylene Dichloride
(EDC) & Others), By Region (Asia-Pacific, North America, Middle East & Africa, Europe and
South America), Competition Forecast and Opportunities, 2011 - 2025. (n.d.). Retrieved from
https://www.techsciresearch.com/report/global-ethylene-market-by-end-use-polyethylene-pe-
ethylene-oxide-ethylene-dichloride-edc-others-by-region-asia-pacific-north-america-middle-east-
africa-europe-and-south-america-competition-forecast-and-opportunities/804.html

6.3 Methanol Market Survey

(Czarina)

Methanol (CH3OH) is a liquid chemical (clear in colour) that is water soluble and biodegradable
and is usually manufactured from synthesis gas (carbon monoxide and hydrogen). The synthesis
gas is converted to methanol at high pressure and temperatures in a fixed bed reactor using a
alumina pellet coated with copper and zinc oxide as the catalyst.

Methanol is used to produce other chemical derivatives, which are then used to produce products
such as plastics, foams, building materials, resins, paints, polyester and pharmaceutical products.
Methanol is also used as an alternative fuel.

Figure 14- Showing Uses of Methanol

The demand for methanol has been increased every year for the past 20 years and is projected to
continue growing. This increase in demand can be credited to the prolific application of
methanol as a fuel. Traditionally, methanol was used mainly as feedstock in the manufacturing of
formaldehyde and acetic acid. Now, a large volume of methanol is consumed in projects such as
olefin production (MTO).

Figure 15- Global Demand of Methanol for 2000-2016 and Projections for 2017- 2020
Figure 16- Methanol Demand by End Application.

Methanol currently costs $550 USD/ Ton and suppliers include:

 Methanex

 Methanol Holdings (Trinidad) Limited

 QAFAC- Qatar Fuel Additives Company Limited

 Ecofuel- Eni

References

(Member Companies. (n.d.). Retrieved from https://www.methanol.org/member-companies/)

Retrieved from https://chemweek.com/CW/Document/80172/The-changing-face-of-the-global-

methanol-industry) (Lazonby, J. (n.d.). Methanol. Retrieved from
http://www.essentialchemicalindustry.org/chemicals/methanol.html)

(The changing face of the global methanol industry. (n.d.). Retrieved from
https://chemweek.com/CW/Document/80172/The-changing-face-of-the-global-methanol-
industry)
 Mass and Energy Balances

7.1 Reactor Mass and Energy Balance

(Jillian)

A summarized description of the calculations performed for the design of the Fluidizing-Bed
Reactor is outlined below, for more details “Ref to Jillian Estwick Reactor Design (FBR) excel
Sheet”.

Mole Balance
Step 1: It was assumed that the products selectivities found in literature, (Salkuyeh & Adams II,
2015, pg 3746), was equal to the stoichiometric coefficient of each component present within the
balanced equation. Since no selectivity data was provided for carbon-dioxide a molar
composition of 0.010 mols/s of CO2 was assumed to be produced for every 1mol of CH3OH
reacted. And since it is proven that higher conversions are achieved with the presence of water in
the feed stream a 1:1 molar ratio of methanol to water was assumed for the reactants. Based on
these assumptions an atomic balance was performed and the overall balanced equation derived.

Overall reaction:

2.687 CH3OH + 2.687 H2O → 0.013 CH4 + 0.431 C2H4 + 0.008 C2H6 + 0.418 C3H6 +0.005 C3H8
+ 0.108 C4H8 + 0.017 C5H10 + 5.385 H2O + 0.010 CO2

Step 2: A target goal of six thousand tonnes (6000 tons) of propylene produced annually was set.
Thus, the molar flowrate of propylene required to exit the reactor to meet this demand was
therefore calculated and found to be 5.009 mols C3H6/sec.

Step 3: The amount of methanol needed to be fed into the reactor to produce the desired molar
flow rate of propylene was subsequently calculated, followed by the number of moles for both
reactants and products using the stoichiometric coefficients and the molar flow rate of methanol.

𝑆𝑡𝑖𝑜𝐶𝐻3𝑂𝐻 𝑚𝑜𝑙𝑠
𝑥 5.009𝑚𝑜𝑙𝑠 𝑜𝑓 𝐶3𝐻6/ sec = 32.2 𝐶𝐻3𝑂𝐻
𝑆𝑡𝑖𝑜𝐶3𝐻6 𝑠𝑒𝑐
Energy Balance:
Step 4: The reference temperature was taken at 25oC since all heats of formation is given at this
temperature. The heat of reaction was calculated using heat of formations data and the
stoichiometric coefficients of both reactants and product. Using the formula outlined in, Folger,
H. S. (1999), the heat of the reaction was found to be -198.1kJ/mol.

Where:

Step 5: It was assumed that there was no Potential energy and kinetic energy within the system,
and since there is no shaft at work Ws was also = 0 (Folger, H. S. 1999). Based on this
assumption the change in enthalpy produced for both inlet and outlet was calculated by
integrating the heat capacity (Cp), between the limits of the reference temperature and the
operating temperature. These enthalpies were then used along with the number of moles of each
component, the heat of the reaction and the stoichiometric coefficient of the base compound. (Ref
to excel data sheet for Cp data and excel sheet for calculations). It was hence determined that
Q (KW) = -855.3

References

Salkuyeh. K and Adams II. A. (2015). Co-Production of Olefins, Fuels, and Electricity from
Conventional Pipeline Gas and Shale Gas with Near-Zero CO2 Emissions. Part I: Process
Development and Technical Performance

Fogler, H. S. (1999). Elements of chemical reaction engineering. Upper Saddle River, NJ:
Prentice Hall PTR.
 7.2 Absorption Column Mass and Energy Balance

(Czarina)

Material Balance:

The column was designed to remove 90% of CO2 from the feed before further separation at an
Operating Temperature of 25 ℃ and a Pressure of 1atm. Mole fraction of CO2 was calculated to
determine if the system was dilute or concentrated (See Absorber Sheet Cell 43 – 59).

A Mass Balance was then performed on the basis of 90% Removal to determine the Mole
Fraction of CO2 leaving the absorber (y2).

7.3 De-Propanizer Column Mass and Energy Balance

(Rachel Kalliecharan)

MASS BALANCE:

(Refer to the ‘Rachel Kalliecharan’ excel file in the ‘De-Propanizer’ excel sheet)

In order to perform a mass balance, the light key and heavy key components are to be identified,
the flow rate of each component entering the column obtained, and the percentage recovery at
the tops and bottoms product need to be specified. In the De-Propanizer Column, the light key
and heavy key components were propane and butene respectively. The percentage recovery of
propane at the tops was 75%, where the trace amount of propane at the tops was an impurity, and
the percentage recovery of butene at the bottoms was 99.5%.

Table 3- De- Propanizer Mass Balance

Performing A Mass Balance on the De-Propanizer

Componen xf Fxf Dxd xd Wxw xw

t
C3H6 0.7618 4.9840 4.9840 0.9898 0.0000 0.0000
 C3H8 0.0092 0.0600 0.0450 0.0089 0.0150 0.0100
C4H8 0.1978 1.2940 0.0065 0.0013 1.2875 0.8546
C5H10 0.0312 0.2040 0.0000 0.0000 0.2040 0.1354
Total 1.0000 6.5420 5.0354 1.0000 1.5065 1.0000

Therefore, the feed entered the distillation column at a flow rate calculated by finding the sum of
all the individual component flow rates which amounted to 6.542 mol/s.

For the flow rate in mol/s of each component entering the distillate stream, the following
deductions were made:

1. 100% of the propylene (C3H6) entered the tops stream

2. 75% of the propane (C3H8) entered the tops stream (from percentage recovery)
3. 0.5% of butene (C4H8) entering the tops stream was calculated by performing a
component balance
4. 0% of the pentene (C5H10) entered the tops stream

For the flow rate in mol/s of each component entering the bottoms stream, the following
deductions were made:

1. 0% of the propylene (C3H6) entered the bottoms stream

2. 25% of propane (C3H8) entering the bottoms stream was calculated by performing a
component balance
3. 99.5% of butene (C4H8) entered the bottoms stream.
4. 100% of the pentene (C5H10) entered the bottoms stream

The flow rates for each component in the tops and bottoms stream were calculated and the tops
and bottoms flow rates were calculated by finding the sum of all the individual component flow
rates which amounted to 5.035 mol/s and 1.507 mol/s respectively.

ENERGY BALANCE:

(Refer to the ‘Rachel Kalliecharan’ excel file in the ‘Condenser Duty’ excel sheet)

To obtain the Temperature entering (Tin) and leaving (Tout) the condenser of the distillation
column, a dew point and bubble point calculation was performed respectively, on the Distillate.
In order to do this, Antoine’s constants were placed in Antoine’s equation and a suitable
temperature was placed in order to obtain the vapor pressure of each component which when
divided by the total pressure, yielded the k values according to Raoult’s Law.

To get the bubble point temperature, the product of the tops number of moles and the k values
was obtained for each component where the sum was calculated as being 1.0 using goal seek.
This suitable temperature was calculated as being -47.9°C. To get the dew point temperature, the
tops number of moles was divided by the k values for each component where the sum was
calculated as being 1.0 using goal seek. This suitable temperature was calculated as being -
47.9°C.

The Tin and Tout were the same values owing to the fact that it was almost pure C3H6, where the
reference state was in the gaseous phase. Since the reference temperature was taken as the inlet
temperature, Tin, the Hout is the change in enthalpy (Hout - Hin) where Hin was therefore zero (0).
The change in enthalpy (Hout) for the gas was calculated as being -18.41 kW. The Duty on the
condenser was then calculated as being -300.3 kW, using the appropriate equation.

REFERENCES

Sinnott, R. K., Coulson, J. M., & Richardson, J. F. (2005). Coulson & Richardson's chemical
engineering. Oxford: Elsevier Butterworth-Heinemann.

Perry, R. H. and D. Green, eds., Perry’s Chemical Engineering Handbook (7th ed.),
McGrawHill, New York, 1997.

7.4 De-Methanizer Column Mass and Energy Balance

Material and energy balance write up (Andrea)

Refer to excel file “Andrea Calculation” sheet “de-methanizer”

We obtain the feed flow coming from the tops product of the de-ethanizer distillation column.
Here a 99.9% purity of methane was specified to be recovered from the top of the De-
methanizer. In order to obtain the flow rates of the bottom and top product along with the mole
fraction for each component of each stream, an overall material balance and a component
balance with respect to the methane component was done.

Table 4- Flow Rates

Parameters Values Units

Feed flow 5.400 Mol/s
Tops product flow 0.150 Mol/s
Bottoms product flow 5.270 Mol/s

Table 5- Mole fraction and Molar flows

Component Inlet mole Inlet molar Distill Distill Bottoms Bottoms

fraction flow mole mole flow mole mole flow
(mol/s) fraction (mol/s) fraction (mol/s)
CH4 0.029 0.155 0.999 0.150 0.001 0.005
5.141C2H4 0.095 5.141 0.0003 0 0.976 5.141
C2H60.9 0.018 0.095 0.0002 0 0.018 0.095

Performing an energy balance, we were able to fine the heat of the reboiler and condenser for the
De-methanizer. The values are shown below

Refer to excel file “Andrea Calculation” sheet “Reboiler”

Table 6- Heat Needed for Equipment

Parameters Values Units

De-methanizer condenser -84.68 Watts
De-methanizer reboiler 78860000.0 watts

Table 7-Heat needed for reboilers

Column Parameters Value Units

De-ethanizer Reboiler heat needed 280200 Watts
De-propanizer Reboiler heat needed 107600 watts
Reference:

Sinnott, R. K., Coulson, J. M., & Richardson, J. F. (2005). Coulson & Richardson's chemical
engineering. Oxford: Elsevier Butterworth-Heinemann.

Perry, R. H. and D. Green, eds., Perry’s Chemical Engineering Handbook (7th ed.), Mc-
GrawHill, New York, 1997.

Equipment Design Calculations

8.1 Reactor Design calculations

(Jillian)

The methanol to olefins (MTO) process comprises of two main steps. The methanol to Dimethyl
Ether (DME) intermediate step, followed by the conversion of DME to olefins. The production
of propylene is achieved via the dehydration of methanol over an H-SAPO34 zeolite type
catalyst.

Step 1: A fluidizing bed reactor is a type of continuously stirred tank reactor (CSTR). Therefore,
the design equation for a CSTR was used since the reaction is steady state and there is little to no
variation in the conditions and reaction rate throughout, this is given in Fogler, H. S. (1999), in
terms of conversion as:

𝐹𝐴𝑂 𝑋𝐴
W= −𝑟𝐴 ′

The rate law for the MTO process was taken from Jianglong & Huixin. (2013) and is shown below.

 The parameters needed to solve the kinetic model for the MTO process, over H-
SAPO34 catalyst was then calculated.
 Where:
XA = Mass of Oxygenates formed, on a water free basis = 455.6 g
XW = Mass fraction of Water on a water free basis = 2.536
Ꝋ = 0.281
Ki = Rate constant = 35.1 hr-1

The rate equation was subsequently solved, and the weight of catalyst required for the bed was
found to be 171,159kg.

Step 2: Next the reactor volume was calculated using the design equation for an FBR when the
reaction is steady state and there is little to no variation in the conditions. Fogler, H. S. (1999)

𝑊
𝑉 = 𝜌𝑏𝑢𝑙𝑘

Where: W=Weight of Catalyst(kg)

ρbulk = Bulk density of the catalyst (kg/m3)

Giving a Bulk Density of 675.00 kg/m3 and Reactor Volume of 254 m3.
Since the calculated reactor volume was very large, it can be presumed that reactor size is
not very unrealistic for industrial applications and therefore needs to be reduced.

Step 3: Using the minimum fluidization velocity equation taken from Dr. M. Watson,
Fluidization, UOPS410B lecture notes, the minimum fluidizing velocity of the bed was
calculated as (μo ) = 0.215 mPa.s.

 s    g D 2 3
uo  o

180  2 1   o 
Step 4: Since the molar flowrate entering the bed was known, the volumetric flowrate of the gas
entering the FBR reactor was calculated using the Ideal Gas Law. This was value was found to
be 0.0901m3/s.
Step 5: Given that Volumetric flow rate = minimum fluidization velocity x Ac, assuming
cylindrical shape of the reactor. The area of the bed was calculated giving a value of 0.419 m2.

Step 6: Having calculated the area of the bed, the diameter was found to be 0.731 m.

Step 7: Next the height of the reactor was found, and is shown below:

Table 8- Calculated Height Reactor

H (m) = Vol. /(pi x rad2) 604.6 m

Bottom cone head height allowance = 1.5 m
Top dome head height allowance = 0.5 m
Total height of Reactor = 606.5

Due to the unrealistic reactor volume previously calculated, the height of the reactor was
also very large. This is expected due to the direct relationship between the Reactor's volume
and its Height. As stated in chapter seventeen (17), section four (4) of the Perry’s Handbook
Fluidizing bed heights are generally not less than 0.3 m or more than 15 m.
References

Fogler, H. S. (1999). Elements of chemical reaction engineering. Upper Saddle River, NJ:
Prentice Hall PTR.

Pu Jianglong & Weng Huixin. (2013). Kinetic Modeling of Methanol to Olefins (MTO) Process
on SAPO-34 Catalyst. Journal of East China University of Science and Technology, Shangha.

Dr. M. Watson, UOPS410B, Fluidization, lecture notes.

Sinnott, R. K., Coulson, J. M., & Richardson, J. F. (2005). Coulson & Richardson's chemical
engineering. Oxford: Elsevier Butterworth-Heinemann.

Perry, R. H. and D. Green, eds., Perry’s Chemical Engineering Handbook (7th

ed.), McGrawHill, New York, 1997.
MECHANICAL DESIGN OF FBR

Since the reactor operates at high pressure, (40 bars) a pressure vessel design was then performed
to determine the thickness of the shell and the mass of steel required for the calculated volume of
the reactor and subsequently costed.

Step 1: The design pressure was calculated to determine the maximum pressure to which the
reactor could be subjected to in operations. Where for vessels under internal pressure the design
pressure is taken at 5 to 10% above working pressure. Coulson and Richardson, Vol 6 (2005).
Design Pressure was calculated to be 44 bars.

Step 2: The design temperature was taken 50 C above the reactor operating conditions to allow
for any uncertainty involved in predicting vessel wall temperatures. Giving a design Temperature
of 450 C.

Step 3: The Minimum thickness of cylindrical section was calculated and found to be 127.7 mm
or 5.03 inches.

Step 4: Having established the wall thickness of the vessel the outer diameter was subsequently
calculated, along with that the internal and external volume of the FBR, assuming a bed height of
10m.

External Diameter of Reactor = 0.9860 m

External Volume of Reactor = 7.64 m3

Internal Volume of Reactor = 4.19 m3

Step 5: Using the density of low alloy steel and the difference between the bed’s external and
internal volume, the mass of material required to fabricate the fluidizing bed reactor was
calculated and subsequently costed.

Volume of Vessel shell = 3.44 m3

Given that the density of Low Alloy Steel = 7850 kg/m3
Mass of material required =27.0 tons
 Cost of FBR (US$) = $338,107
Cost of Catalyst (US$) = $25,674

Fluidizing Bed Reactor Sensitivity Analysis

Table 9- Sensitivity Data for Reactor

SENSITIVITY DATA

kw Volume of Reactor Wt.of Catalyst Height of Reactor

0.00 71.2 48066 173
0.51 162.4 109612 393
1.01 253.6 171159 613
1.52 344.7 232705 832

Volume vs Kw
400.0
344.7
350.0

300.0
253.6
250.0
volume

200.0 162.4
150.0

100.0 71.2

50.0

0.0
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60

Kw

Volume Linear (Volume)

The presence of water in the feed has a great effect on the product selectivity and reaction rate in

the MTO process. Methanol concentration influences the catalytic performance, resulting in

decreased reaction rates, higher total active time, higher yields and improved selectivity of light
olefin when methanol feed concentrations are low. It should be noted however that the exact

opposite occurs when high methanol concentrations are utilized within the feed stream. Because

a 50/50 CH3OH to H2O mole% feed was used in the fluidizing bed reactor, it is safe to assume

that the presence of water decreased the overall rate of reaction. For the design of the reactor, the

effect of water resistance was quantified by the function θ, where θ=1/1+Kw Xw.

In the equation, Kw is a parameter that quantifies the water resistance for the reaction rate, and

Xw is the water content in the reaction medium which is the weight fraction (on a water-free

basis) of water in the reaction medium. A sensitivity analysis was then performed by varying K w

to determine the effects on the Fluidizing bed Reactor. However, for the purpose of this analysis

greater emphasis will be placed on the effects of the reactor’s volume more specifically.

The reactor volume was seen to have increased as Kw increased, this is due to the dilution of the

methanol concentration in the feed stream, resulting in the competition between the different

basic species for the Brønsted acid sites. Since water is more basic than that of methanol and

olefins, water is more likely to inhabit stronger acid sites, leaving less and weaker acid sites in

the catalyst, hence lowering the overall rate of conversion. Since our percent conversion (99.9%)

was fixed into our reactor design model, the mass of catalyst required to satisfy that conversion,

would increase of decrease with respect to the water resistance parameter (Kw). Therefore, based

on our sensitivity analysis volume is expected to increase to accommodate the increased mass of

catalyst, creating a direct relationship between reactor volume and water resistance (Kw).

References

Dr. M. Watson, UOPS410B, Fluidization, lecture notes.

Sinnott, R. K., Coulson, J. M., & Richardson, J. F. (2005). Coulson & Richardson's chemical
engineering. Oxford: Elsevier Butterworth-Heinemann.
 8.2 Absorption Column Design Calculations
(Czarina)

Calculating Liquid Flowrate:

The next step was to determine the Liquid Flowrate entering the column. This was done by
constructing a x-y Diagram comprising of an Equilibrium Line, L/Gmin Line and Operating Line
to determine x1max, Ls, x1, and L. x1max is the maximum concentration of CO2 that can be removed
and is taken at the point in equilibrium y2.
Equilibrium data for MEA at 25 ℃ and 1 atm was utilized to plot the Equilibrium Line. (See
Absorber Sheet Cell 80-112). The L/Gmin Line (operating line at max CO2 Removal) was
constructed using the mole fraction at the Bottom of the Column ( x1max, y1) and at the Top of the
Column (x2, y2) and Minimum Liquid Flow was calculated.
This equation was derived from the Operating Line Equation of a Dilute System:
𝐺𝑠 (𝑦1 − 𝑦2 ) = 𝐿𝑠 (𝑥1 − 𝑥2 )
where: Gs is the Gas Flowrate excluding that of the component to be removed
Ls is the Liquid Flowrate excluding that of the component to be removed
𝐺𝑠 = 𝐺(1 − 𝑦1 ) 𝐿𝑠 = 𝐿(1 − 𝑥1 )
The calculated minLs was multiplied by a factor of 1.5 to obtain Ls and the equation for Ls was
rearranged to solve for L. The Operating Line equation was then rearranged to solve for x 1.
The Operating Line Equation was constructed using x1, y1 and x2, y2 and the Number of Stages
were determined by stepping off the Operating Line to the Equilibrium Line. See Absorber Sheet
Cells 115-182 for all calculations regarding Liquid Flowrate and x-y Diagram.
Calculating Diameter of Absorber:
Firstly, Gas and Liquid Flowrates were converted to Mass Flowrates. (See Absorber Sheet Cell
184-219). Packing type and size were chosen and Packing Parameter were obtained. (See
Absorber Sheet Cell 224-227). A graph correlating Pressure Drop with Flow Factor (FLV) and K4
(was utilized to obtain K4. FLV was then calculated. Recommended Range for pressure drop of an
Absorber is between 15 -50 mmH2O ( Ref. Coulson and Richard- Vol. 6 Chap 11 pg 602) so a
value of 20mmH2O ( within range) was chosen. Minimum Limit of FLV on graph was used since
calculated value was unavailable on this correlation. K4 was obtained at FLV = 0.02 and Pressure
Drop = 21mmH2O and K4 @ Flooding Line was also obtained, and Flooding Percentage was
calculated. ( See Absorber Sheet Cell 228-326)
Mass Flowrate per Unit Cross Sectional Area (Gw*) was calculated and utilized to calculate
Column Area Required (S). Diameter was then calculated from the Area. (See Absorber Sheet Cell
330 – 351)
Calculating Height of Packing:
Resistance was calculated and it was concluded that for this design Absorption would take place
in the gas phase. The Height and Number of Transfer Units were calculated, and their product gave
the Height of Packing (z). (See Absorber Sheet Cell 353-463 for calculations)
Calculating Height of Column:
A correlation was used to calculated height of Column.

Pressure Vessel Design:

Pressure Vessel was Design on the Fourth Sensitivity Analysis (See Sensitivity 4 Sheet Cell
438 - 680). Design Pressure was calculated, and Joint Type was chosen. The material for Vessel
was selected factoring minimum thickness required and cost of the material. Minimum thickness
for 3 different materials were calculated and Carbon Steel was selected as it was the cheapest of
all three. Ratio was then calculated, and it was concluded that the vessel was thin walled. As such,
Principal Stresses to be considered were Circumferential and Longitudinal and these were
calculated along with the Maximum Shear Stress. Next, the type of Vessel head was selected by
selecting the vessel head with its calculated minimum thickness closest to the of vessel body. An
Ellipsoidal Head was chosen. Finally, the Critical Buckling Pressure of the Vessel was calculated
to determine if the PV Design could support the Design Pressure without failure.

Sensitivity Analysis:
A Sensitivity Analysis was conducted to investigate the effect of concentration of CO2 in feed to
the Diameter size of the Column. The mole fraction of CO2 entering the column was increased up
to 10% to determine if Column Diameter would increase as current diameter was relatively small.
This max value of 10% was used to keep the assumption of the Dilute System Valid. Upon analysis
of the results it can be seen that Column Diameter is directly related to the amount of CO2 entering
the system. However, there is no significant increase in diameter. Feed Flowrate may be another
factor affecting Column diameter and increasing feed may also increase the size of diameter
however, in this system feed flowrate is fixed.

0.49500
0.49000 Mole Fraction of CO2 vs Column Diameter
Column Diameter, m

0.48500
0.48000
0.47500
0.47000
0.46500
0.46000
0.0000 0.0100 0.0200 0.0300 0.0400 0.0500 0.0600 0.0700 0.0800 0.0900 0.1000
Mole Fraction of CO2

Figure 17- Sensitivtiy Analysis of Column Diameter

8.3 De-Propanizer Column Design Calculations and Sensitivity

DESIGN CALCULATIONS ON THE DE-PROPANIZER COLUMN (Rachel)

(Refer to the ‘Rachel Kalliecharan’ excel file in the ‘De-Propanizer’ excel sheet)

By performing a mass balance on the column, the number of moles for each component in the
feed, distillate and bottoms streams were successfully obtained. Using this information, a bubble
and dew point calculation was performed using the bottoms and tops mole fractions for each
component respectively.

Placing Antoine’s constants into Antoine’s equation and using a suitable temperature, the vapor
pressure of each component which when divided by the total pressure, yielded the k values
according to Raoult’s Law. Using goal seek, the bubble point temperature was calculated as
being -4.6°C and the dew point temperature was calculated as being -47.8°C.

The average relative volatility value was calculated by finding the average ratio of the light key k
value to the heavy key k value. This value was then calculated as being 4.59. The relative
volatility value provides an estimate on the degree of separation. If the value is very close to one,
the separation is more difficult and the cost increases because a larger column and energy input
would be required. Initially, propylene was to be separated from propane, however, the relative
volatility was extremely close to one and therefore to provide a greater degree of separation,
propane was separated from butene instead where the percentage of propane in the overhead
product was taken as an impurity in the stream.

The reflux ratio was calculated using the Underwood Equation which required the value of q,
which is the fraction of the feed that is liquid. Therefore, to obtain this value, a bubble and dew
point calculation was performed using the feed number of moles to obtain the temperature of the
liquid and vapor respectively which was found to be -42.9°C and -23.4°C respectively. Since the
feed entered the column at a temperature of 90.4°C, which was higher than the temperature of
the vapor, it was understood that the feed was in the vapor phase. This was then confirmed with
the negative value of q of -0.85.

For the Underwood equation, a value of theta, whose value needed to lie between the relative
volatility of the light and heavy key values was required, which was obtained using goal seek
and was found to be 3.46. This theta value was then used to solve the minimum and actual reflux
ratio which was found as being 1.49 and 2.24 respectively.

The minimum number of stages was then calculated using Fenske’s equation as being 4.2 stages.
The theoretical number of stages was then found using the Eduljee, Chung and Molkanov
correlations where the value of X was found using the minimum and actual reflux as being 0.23.
The Eduljee, Chung and Molkanov correlations yielded 8.02, 7.81 and 8.20 stages respectively.
The Molkanov correlation obtained the greatest number of stages of 8.20 stages and was chosen,
being the worst-case scenario.

The average relative viscosity found to be 0.06 mNs/m², using an appropriate correlation. This
value, together with the average relative volatility value calculated, was used in the O’Connell’s
correlation to obtain an efficiency of 69.95%. Using the efficiency calculated and the theoretical
stages found, where one stage was designated for the reboiler, the actual number of stages which
was found to be 10.44 stages.

The tops vapor density of the column was calculated using the ideal gas law and the mole
fractions of the distillate and was found to be 2.25kg/m3. The tops liquid density of the column
was calculated using the pure liquid densities for each component and the mass fractions of the
distillate and was found to be 611.7kg/m3. The bottoms vapor and liquid densities were
calculated in a similar manner and was found to be 2.59kg/m3 and 602.3kg/m3 respectively.

Using a tray spacing of 0.5m, a top and bottom allowance of 1m each and the actual number of
trays as 10.44 trays, the column height was found as being 7.22m. To solve for the diameter of
the column, the maximum allowable vapor velocity and the maximum vapor rate was required.
Using the tray spacing of 0.5m and the vapor and liquid densities calculated, the maximum
allowable vapor velocity was calculated as being 0.745m/s. The maximum vapor rate was then
calculated as being 0.687kg/s. The diameter and area of the column was then found to be 0.723m
and 0.41m2 respectively using the appropriate equations provided.

HYDRAULIC PLATE DESIGN

(Refer to the ‘Rachel Kalliecharan’ excel file in the ‘De-Propanizer’ excel sheet)

The hydraulic plate design was done to ensure that the plate provided: proper vapor to liquid
contact; adequate liquid hold-up to ensure favorable mass transfer which is indicated by a high
efficiency; adequate area and spacing to ensure the entrainment and pressure drop was within the
acceptable limits and; adequate downcomer area to allow the free flow of the liquid from plate to
plate.

An initial assumption of 100mm of water for the pressure drop was used as the first iteration.
The vapor flow rates for the tops and bottoms were found as being 0.687kg/s each using the
appropriate equations. The liquid flow rates for the tops and bottoms were found as being
0.475kg/s and 0.774kg/s respectively using the appropriate equations. The liquid to vapor flow
factor (FLV) for the enriching and stripping sections was calculated as being 0.042 and 0.074
respectively. These values were found by substituting the liquid and vapor mass flow rates as
well as the liquid and vapor densities into the FLV equation.

Using the tray spacing of 0.5m and the FLV values calculated, the constant K1 values were
obtained from the ‘Flooding velocity, sieve plates’ graph as being 0.09 for the tops and 0.085 for
the bottoms. In order to calculate the corrected K1 values, the surface tension values for the tops
and bottoms were required and were calculated as being 8.34×10-3N/m and 7.83×10-3N/m
respectively. Therefore, the corrected K1 values for the tops and bottoms were found to be 0.076
and 0.071 respectively.

The flooding vapor velocity was then calculated using the equation provided as being 1.072m/s
at the bottoms and 1.244m/s at the tops. However, the column was designed for 85% flooding at
the maximum flow rate. Considering this, the flooding vapor velocity was then as being
0.911m/s at the bottoms and 1.06m/s at the tops. The maximum volumetric flow rate for both
tops and bottoms were then found as being 0.306m3/s and 0.265m3/s by dividing the vapor flow
rates by the vapor densities. The maximum volumetric liquid rate was found to be 1.29×10-3m3/s.
In using the ‘Selection of liquid-flow arrangement’ graph, it was clear that reverse flow can be
used.

The net area required for the tops and bottoms was calculated as being 0.289m2 and 0.291m2
respectively. The column cross sectional area was found as being 0.328m2 at the tops and
0.331m2 at the bottoms using the net area calculated and the downcomer area as 12% of the total
area. The column diameter was then found as being 0.649m at the bottoms and 0.647m at the
tops, using the column’s cross-sectional area. Therefore, the bottoms diameter of 0.649m was
used in the provisional plate design calculations.

Table 10- values for the provisional plate design:

Property Value Unit

Column diameter, Dc 0.649 m
Column area, Ac 0.331 m2
Down-comer area, Ad (at 0.040 m2
12% column area)
Net area, An 0.291 m2
Active area, Aa 0.251 m2
Hole area, Ah (at 7% active 0.018 m2
area)

The weir length was then calculated using the percentage of the ratio of the downcomer area to
the column area to read off the x axis of the ‘Relation between downcomer area and weir length’
graph. This x axis was then multiplied by the column diameter to achieve a weir length of
0.487m.

Weeping is a phenomenon which is caused due to a low vapor flow. This occurs when the
pressure exerted by the vapor is insufficient to hold up the liquid on the tray. This results in the
liquid leaking through the perforations or holes. The actual minimum vapor velocity at 10.55m/s
was larger than the minimum vapor velocity at 7.42m/s. This indicated that the minimum
operating rate will be well above weep point.

The total pressure drop is taken as the sum of the pressure drop calculated for the flow of vapour
through the dry plate (the dry plate drop hd); the head of clear liquid on the plate (hw + how); and
a term to account for other, minor, sources of pressure loss referred to as the residual loss hr.

Table 11- values for the total plate pressure drop calculation

Property Value Units

hw+how 64.33 mm of liquid
hd 72.35 mm of liquid
hr 20.75 mm of liquid

The total plate pressure drop, ht was calculated as being 157.4 mm of liquid and the column
pressure drop was calculated as being 16119 Pa.

REFERENCES

Sinnott, R. K., Coulson, J. M., & Richardson, J. F. (2005). Coulson & Richardson's chemical
engineering. Oxford: Elsevier Butterworth-Heinemann.

Perry, R. H. and D. Green, eds., Perry’s Chemical Engineering Handbook (7th ed.),
McGrawHill, New York, 1997.
SENSITIVITY ANALYSIS FOR DE-PROPANIZER COLUMN (Rachel)

(Refer to the ‘Rachel Kalliecharan’ excel file in the ‘Sensitivity Analysis’ excel sheet)

The distillation process is done to achieve a specific level of enrichment or purity. In order to
achieve this enrichment level, one must specify a reflux ratio. The reflux ratio is known as the ratio
between the amount of reflux that goes back down the distillation column and the amount of reflux
that is collected in the receiver or the distillate. For this sensitivity analysis, the reflux ratio was
increased to observe the effect on the number of trays, diameter, duty of the condenser as well as
the impact it would cause on the overall cost.

With the increase in reflux ratio is increased, there would be more vapor to liquid contact occurring
in the distillation column. This suggests that the higher reflux ratios lead to higher purity of the
distillate. However, it also leads to the collection rate for the distillate being slower which is
confirmed by the reflux ratio equation which shows that the reflux ratio is inversely proportional
to the distillate rate.

Table 12- De-Propanizer Sensitvity

For the De-Propanizer Sensitivity:

Cost of one $656.00
tray, $USD
Reflux Height of Diameter, Number of Duty of Cost,
Ratio Column, m m Trays Condenser, $USD
kW
2.239 7.220 0.649 10.439 -300.270 $13,424.81
10.000 4.753 1.196 5.506 -1019.719 $12,349.83
15.000 4.601 1.442 5.202 -1483.228 $13,836.93
20.000 4.528 1.652 5.056 -1946.737 $15,218.92
 Height of column and Diameter vs Reflux Ratio
8.000 2.000
Height of column/m

6.000 1.500

Diameter/m
4.000 1.000

2.000 0.500

0.000 0.000
0.000 5.000 10.000 15.000 20.000 25.000
Reflux Ratio

Height of Column,m Diameter, m

Figure 18-Showing the relationship between reflux ratio and the height and diameter of the column

Based on Figure 1.0 above, it is seen that with the increase in the reflux ratio there was a decrease
in the height of the column. As aforementioned, when the reflux ratio is increased, more
enrichment or percentage purity is achieved owing to the increase in the vapor to liquid contact in
the distillation column. As a result of this, separation becomes better and thus less trays are needed
to achieve the same degree of separation. The decrease in the number of trays would then lead to
a decrease in the height of the column.

On the other hand, when the reflux ratio was increased, the diameter of the column increased as
well. The increase in the reflux ratio results in an increase in the liquid reflux, that is rich in the
more volatile components, being recycled back into the column. Therefore, a larger diameter is
required to handle this increased liquid reflux. Based on the costing of the column, the larger
diameter of the column would also increase the cost of the column.
 Cost/$USD vs Reflux Ratio
$15,500.00
$15,000.00
$14,500.00
$14,000.00
Cost/ $USD

$13,500.00
$13,000.00
$12,500.00
$12,000.00
$11,500.00
$11,000.00
0.000 5.000 10.000 15.000 20.000 25.000
Reflux Ratio

Figure 19- Showing the relationship between reflux ratio and the cost of the column

In Figure 2.0, it is seen that as the reflux ratio increased, the cost also increased. However, it was
seen that at the reflux ratio of 10, there was a plummet in the cost of the column. As reflux ratio
increases, less stages are required but it was noted that the equipment needed to be larger to
facilitate the increased liquid reflux and the reboiler vapour load. Therefore, the cost
decreased but experienced an increase when the reflux ratio approached total reflux.

Condenser Duty vs Reflux Ratio

Reflux Ratio
0.000 5.000 10.000 15.000 20.000 25.000
-500.000
Condenser Duty, kW

-1000.000

-1500.000

-2000.000

-2500.000

Figure 20- Showing the relationship between reflux ratio and the duty of the condenser

Increasing the reflux ratio decreases the distillate rate. This poses a disadvantage because it causes
the duty of the condenser and reboiler to increase, due to an increase in the load in the distillation
column, since less mass goes out as distillate rate. Therefore, this increases operating costs with
the additional heating (reboiler) and cooling (condenser) required. From Figure 3.0, it is seen that
an increase in the reflux ratio caused an increase in the condenser duty where the negative sign
indicates heat is added/required.

8.4 De-Methanizer Column Design Calculations and Sensitivity

De-methanizer Equipment write up (Andrea)

Refer to excel file “Andrea Calculation” sheet “de-methanizer”

The light key for the de-methanizer is the methane and the heavy key is the ethylene
Step 1: calculating the temperature of the reboiler using Raoult’s Law. Initially, we calculate the
K values using Antione’s constants. By using goal seek we were able to find the temperature of
the reboiler as show below Using the K values and Raoult’s Law, the temperature of the reboiler
was found at 3.05oC
Step 2: By using the method in step one to find K values the temperature of reboiler was found
to
Step 3: By using the method in step 1 to find K values. The value of the top tray was found to be
-2.66oC and the temperature of the bottom tray was found to be 1.81oC.
Step 4: Calculating the values of the minimum reflux ratio. By using both of underwood equation
to obtain the value of q and Rmin .This was done firstly by calculating the alpha vales of the top
and bottom.
The following values were then calculated
Table 13- Rmin Values

Parameters Values
θ 1.47
q 1.982
Rmin 0.194
The reflux ration was calculated at a factor of 1.5 of Rmin. , where the reflux ratio was found to be
0.291.
Due to the small low rate coming into the column we would get a small R value. To make this
larger, it is recommended that we increase the amount of raw material to make more product
Step 5: calculating the minimum number of trays using Fenske’s equation. This was found to be
a value of 6.834 stages. We then calculated the value of X which was found to be 0.075. This
correlation would be used in Eduljee, Chung and Molkanov equations to find the theoretical
number of stages
Taking the worst-case scenario, we used the value found form Eduljee’s equation, therefore the
theoretical number of stages was found to be 17.5 stages.
Step 6: we calculate the actual temperature of the condenser since it is a partial condenser that
would be used for this process. This calculation was done by performing a flash calculation
on the condenser. The actual temperature was found to be -84.88oC.
Step 7: Calculating overall column efficiency and actual number of trays for the de-
methanizer. Prior to the calculation we found the average viscosity of the column which was
found to be 0.023Pa-s
Overall efficiency = 73.43%
In order to calculate the actual number of trays, we use the value from eduljee’s equation. The
reboiler would count as a stage, therefore we would have to minus one from the value found
in eduljee’s equation. Theoretical stages were found to be 16.4 and actual stages was found to be
23
Step 8: calculating the maximum Allowable vapour velocity, and using ls as 0.5m
Uv=0.163m/s
Step9: Calculating the Diameter of the Column. Firstly, calculating the maximum vapour flow
rate in kg/s which was found to be 0.19kg/s. Dc was found to be as shown below
Dc= 0.2m
From this, the height of the distillation column was found to be 14.25m and the area of the
column was found to be 0.149m2.
 Hydraulic plate design
Table 14- surface tension and Average molecular mass

Parameters Tops Bottoms

Surface tension, σm 73.17 78.25
Average molecular mass 16.03 15.96

Assuming a pressure drop of 100mmHg for 1st iteration

Calculating the liquid vapor flow, FLV in order to obtain a valve for K, K was read off Graph---
Table 15- Hydraulic Plate Design

Parameters Values Units

Lw 0.0007 Kg/s
Vw 0.148 Kg/s
FLV 0.01
Plate spacing 0.6
K 0.1
Flooding velocity was calculated to be a value of 0.036m/s. from this we were able to calculate
the column diameter
Table 16- Calculating Column Diameter

Column section Value Units

Percentage of flooding 0.800
Actual velocity 0.029 m/s
Maximum volumetric flow rate 0.059 m3/s
Net area 0.492 m2/s
Cross sectional area 0.559 m2
Column diameter 0.844 m

From calculating the maximum volumetric flow rate, it was found to be 3.01x10-3m3/s. by using
figure __, the flow arrangement was found to be reverse flow.
For the provisional plate design, we look at the table below
Table 17- provisional plate design

Parameters value Unit

Column diameter, Dc 0.844 m
Column area, Ac 0.559 m2
Down-comer area, Ad 0.067 m2
Net area, An 0.492 m2
Active area , Aa 0.425 m2
Hole area, Ah 0.021 m2
With respect to the small diameter would be due to the low feed flow coming into the column. In
order to have a bigger diameter, it is recommended that the flow rate of the raw materials
entering the process is increase to get a more reasonable value.
Finding values of Lw/Dc form figure ___, it was found to be 0.75, where lw would be taken as
0.506.
After we check for weeping. Where the Uhmin was found to be 1.024m/s whereas the actual value
of the minimum vapour velocity was found to be 4.808m/s. With the actual value of weeping is
greater shows that weeping would occur in the Column.
The plate pressure drop was calculated to be as shown in the table below;
Table 18- pressure drop values

Pressure drop Value Units

hw+how 53.8 mm of liquid
hd 47.46 mm of liquid
hf 21.69 mm of liquid
Total pressure drop, ht 123 mm of liquid

The pressure drop throughout the column was found to be 1206.07 Pa.
References
Coulson and Richardsons Volume 6
Perry, Chemical Engineering textbook
Marian Watson Unit operation 2, 2018
Nishawn Hanif, 2019
.
Sensitivity Analysis (Andrea)

Refer to excel file “Andrea Calculation” sheet “Sensitivity table”

To perform a sensitivity analysis on the de-methanizer we vary the reflux ratio and look at the
effect it would have on the column. Reflux ratio values were varied as the following; 0.29, 5, 10,
20.

For the first sensitivity performed, we looked at the reflux ratio and how it affects the height and
the diameter of the column.

Table 19- data of height, diameter and reflux ratio.

Sheet name Reflux ratio Height of column, m Diameter, m

De-methanizer 0.29 14.25 0.190
Sensitivity 2 5 7.49 0.410
Sensitivity 3 10 7.24 0.555
Sensitivity 1 20 7.11 0.766

Column diameter and height vs. reflux ratio

16.00 0.900
14.00 0.800

Column Diameter
12.00 0.700
10.00 0.600
Height

0.500
8.00
0.400
6.00 0.300
4.00 0.200
2.00 0.100
0.00 0.000
0.00 5.00 10.00 15.00 20.00 25.00

0.00 5.00 10.00 15.00 20.00 25.00

Reflux Ratio

height of column,m Column diameter,m

Figure 21- Graph of Column Diameter and height vs. Reflux ratio
 With respect to the diameter of the distillation column, we can see as the reflux ratio increases
the diameter of the column also increases. This is due to a higher reflux flow coming back into
the column as larger equipment is needed to handle the reflux liquid. We can say the relationship
between the reflux ratio and the diameter of the column is directly proportional.

And with respect to the height of the column, we saw that as the reflux ratio increases the height
of the column decreases. This is due to the reflux coming back into the column at a larger rate, it
allows for better contact of liquid and vapour. This allows the components to reach equilibrium
faster, thus decreasing the number of trays. The relationship between the height of the column
and the reflux ratio is inversely proportional.

Secondly, we look at the reflux ratio and how it affects the price of a column

Table of Reflux ratio and Cost.

Table 20- Reflux ratio and Cost.

Sheet name Reflux ratio Costing

De-methanizer 0.29 $9,594.75
Sensitivity 2 5 $7,705.73
Sensitivity 3 10 $9,578.62
Sensitivity 1 20 $12,457.99

Figure 22- Costing vs. Reflux Ratio

For this sensitivity, as we increase the reflux ratio, we saw that the price dropped and then it had
increased. Since the equipment decreased in height but increased in size to handle the load of the
vapour from the reboiler and the liquid from the reflux. This would cause the price to drop as it
reaches the minimum reflux ratio but increase as the reflux ratio tends to infinity.

8.5 Heat Exchanger Design Calculations

(Czarina)

Firstly, the Duty was calculated using the following equation:

𝑄 = 𝑛𝑐𝑝ΔT

where:

Q = Duty

n = Molar Flowrate

ΔT - Change in Temperature

∆𝑇 = 𝑇2 − 𝑇1

cp - Specific Heat Capacity of Component

Specific Heat Capacity of Components in Gas State was calculated using the following equation:

𝐶𝑝 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 + 𝑑𝑇 3

𝐶𝑝 = 𝑎 + 𝑏(𝑇1 − 𝑇2 ) + 𝑐 (𝑇12 − 𝑇22 ) + 𝑑 (𝑇13 − 𝑇23 )

Next, Overall Heat Transfer Coefficient was estimated and Area was calculated using the
following equation:

𝑄
𝐴=
∆𝑇𝑀 𝑈

where:
U- Overall Heat Transfer Coefficient

A - Area of Heat Exchanger

ΔTM -mean temperature Difference = ∆𝑇𝐿𝑀 𝐹𝑡 , 𝑤ℎ𝑒𝑟𝑒 𝐹𝑡 = 1

ΔTLM- Log mean Temperature Difference

These steps were repeated for each Heat Exchanger. (See Heat Exchanger Sheet for all
calculations.)

References:

Sinnott, R. K., & Coulson, J. M. (2005). Coulson & Richardsons - Vol. 6 Chemical Engineering
Design. Amsterdam: Elsevier Butterworth-Heinemann, .

Geankoplis, C. J. (1978). Transport Processes and Unit Operations. Boston: Allyn and Bacon.

Salkuyeh, Y., & Ii, T. (2015). Co-Production of Olefins, Fuels, and Electricity from
Conventional Pipeline Gas and Shale Gas with Near-Zero CO2 Emissions. Part I: Process
Development and Technical Performance. Energies,8(5), 3739-3761. doi:10.3390/en8053739

Process Simulations
Figure 23- Hysys Simulation

Figure 24- Hysys Rigorous Plant

 Hysys Fluidizing Bed Reactor (Jillian)

A Fluidizing Bed reactor (FBR) is a type of Continuously Stirred Tank reactor (CSTR). These
types of reactors are used to perform a variety of multiphase chemical reactions. As a result, it is
now being used in many industrial applications. One such application is for the production of
ethylene and propylene via the Methanol to Olefins (MTO) process. For the purpose of
modelling the reactor in hysys, a Kinetic CSTR was used. For kinetic reactions the kinetic model
is specified for the reactor, where hysys then calculates the rate of reaction per unit volume of the
reactor. The stoichiometric coefficients of the balanced equation, along with the calculated
overall rate constant, activation energy for the dehydration of methanol over H-SAPO34 catalyst,
taken from, P. Grigore (2009), and the calculated volume of the reactor was entered into hysys
and programme ran to generate the following results:
Table 21- Hysys Evaluation of Reactor

Excel Calculated Hysys Computed

Parameters Values Values
Reactor Exit stream flowrate (mols/s) 44.13 43.9
Mole Fraction of Ethylene produced 0.1171 0.102
Mole Fraction of Propylene produced 0.1136 0.099
Height of Reactor (m) 606.5 605.2
Conversion (%) 99 93

Based on the values obtained it could be stated that they are very similar to those calculated.
However, it should be noted that the percent conversion decreased from 99% to 93%. When
fixing the percent conversion at 99%, using a height within the range for FBR and assuming
diameters between 5 and 10 meters, the volume computed was even larger than the calculated
value of 254m3, making it unrealistic.
 HYSYS SIMULATION OF DE-PROPANIZER COLUMN (Rachel)

Table 22- Hysys SImulation of De- Propanizer Column

Parameter De-Propanizer Column Rigorous Model of Units

Excel (Short-Cut the De-Propanizer
Method) Column
Feed molar flow 6.542 6.538 gmol/s
Distillate molar flow 5.035 5.035 gmol/s
Bottoms molar flow 1.507 1.503 gmol/s
Total Pressure 100 100 kPa
Number of stages 11 11
Reflux Ratio 2.24 2.24
Efficiency 69 69 %
Tops Temperature -47.8 -53.32 °C
Bottoms Temperature -4.6 -4.774 °C

There are not much deviations observed in the values generated from the calculations performed
in the ‘Rachel Kalliecharan’ excel file of the ‘De-Propanizer’ excel sheet, which operated like a
short-cut distillation column, to the Rigorous Model of the De-Propanizer Column generated
from Hysys.

Initially, the De-Propanizer column operated at a total pressure of 25 bar. However, a very
unfavorable diameter value was obtained. Therefore, in an effort to optimize the process, the
pressure was reduced to 1 bar and this increased the diameter to a more favorable outcome.

De-Propanizer Column Excel (Short-Cut Method)

Components Formula Feed Composition Tops Bottoms

Composition Composition

Propylene C3H6 0.7618 0.9898 0.0000

Propane C3H8 0.0092 0.0089 0.0100
 Butene C4H8 0.1978 0.0013 0.8546
Pentene C5H10 0.0312 0.0000 0.1354

De-Propanizer Column (Rigorous Model)

Components Formula Feed Composition Tops Bottoms

Composition Composition

Propylene C3H6 0.7381 0.9556 0.0092

Propane C3H8 0.0090 0.0116 0.0003
Butene C4H8 0.1978 0.0017 0.8550
Pentene C5H10 0.0311 0.0000 0.1355

Using the Short-Cut Method, approximations on the feed, distillate and tops compositions are
obtained. Accurate values are achieved using the Rigorous Model where the composition of the
desired product propylene was found to be 0.9556 mol at the tops, which did not deviate much
from the composition using the Short-Cut Method of 0.9898 mol propylene.

Hysys analysis on de-methanizer column. (Andrea)

For the second hysys file we configured rigorous distillation column. here we compare the values
of the short cut distillation column to the rigorous distillation column. the same fluid package was
used in both hysys file for the distillation column.

Table of compared values

Parameters Excel calculating valve Rigorous column valve

Pressure 40 bars 40 bars

Inlet flow rate 5.44mol/s 5.44mol/s

Inlet temperature -9 oC -9 oC

Tops flow rate 0.15mol/s 0.15 mol/s

Tops temperature -2.66 oC -4.515 oC

Bottom flow rate 5.29 mol/s 5.29 mol/s

Bottom temperature 1.808 oC -2.135 oC

As for the both calculated and hysys generated values for the flow rate stayed the same. But the
temperature of the tops and bottom change. This can be due to the efficiency and the number of
trays that was specified in the hysys file. As we can see the was a deviation of 0.327 oC for the
temperature of the bottoms and a deviation of 1.86 oC for the tops.

Table of calculated mole fraction

Components Inlet (mole fraction) top (mole Fraction) bottom (mole fraction)

CH4 0.0287 0.999 0.001

C2H4 0.9491 0.0003 0.976

C2H6 0.0176 0.0002 0.018

Table of Hysys mole fraction.

Components Inlet (mole fraction) Top (mole fraction) Bottom(mole fraction)

CH4 0.0286 0.0857 0.0270

C2H4 0.9230 0.8956 0.9237

C2H6 0.0147 0.0108 0.0148

With a 99.9% purity of ethylene in the De-methanizer, due to the rigorous column we got an purity
of 92% overall. These composition were expected to change since the rigorous columns takes into
account of the efficiency of the trays and also the temperature difference form the calculated values
and the hysys values.

In the hysys model itself, a heat exchanger was added on the stream entering the de-
methanizer inorder to raise the pressure of the stream, and lower the temperature. we also added a
heat exchanger on the stream going into the column of the de-propanizer to lower the pressure of
the stream but keep it at the same temperature.
 Financial Operating Model and Selectivity Analysis

See excel File “Czarina/ Financial Model

Financial Model Results

Production:

Basis:

Revenue:

Utilities and Labor:

CAPEX:

OPEX:

Loss Per Year:

Economic Summary:

The financial model showed that this project was not feasible. Revenue generated was not enough to
breakeven. Optimization to equipment may be done to reduce utility and equipment costs thereby
reducing direct costs.
 Overall Control Strategy

Reactor Control strategy (Jillian)

For the process control strategy, two parameters were chosen, temperature
and pressure. Firstly, we will discuss the controlling of temperature as it pertains to the
reactor. In the P&ID labelled “MTO Reactor P &ID (Jillian)”, the inlet piping identified
as (S1) has two temperature devices, a temperature indicating device (TI-1) and a temperature
transmitting device (TT-2) located both upstream and downstream respectively, of heat
exchanger (E-01). The temperature of the inlet stream before it enters E-01 is monitored using
(TI-1), the purpose of the instrument is to allow the operator to have a basic understanding as to
the temperature of the feed entering the exchanger.
The temperature transmitting device identified as TT-2, relays the temperature of E-01 exit
stream and transmits this signal to the associated flow controller (FIC-2). If the temperature of
the exiting stream is too high a signal will be sent to FIC-2, which gives the order
to increase flow through control valve (V-01). The increased flow rate single pass through the
exchanger should reduce the temperature of the inlet stream (S1) to the reactor. If the
temperature of the exiting stream is too lower the reverse is procedure is done.
There are two temperature devices installed onto the reactor bed, a temperature
indicating controller (TIC-3) and a temperature transmitting device identified as (TT-1). Since
the reaction is to occur under isothermal conditions, a live signal is transmitted from (TT-1) to
(TIC-3) and action taken in cases of fluctuations. If the temperature of the bed increases above
the operating temperature of 400°C TIC-3 send signal to control valve (V-07) which would open
the cooling water line to allow for a greater flow of cooling water into the reactor jacket, thereby
cooling the system.
On the cooling water line (CW-01), which is the inlet stream of the reactor jacket, there is a
temperature indicating controller (TIC-1A), this indicator controls temperature of the reactor
jacket which is set at 25°C. If the temperature of CW-01 is to high a signal will be sent to the
flow indicating controller (FIC-1), which would relay a command to the three (3) powered
valves (V-04), (V-05) and (V-06) respectively to be closed. The cooling water line (CW-
01) would then be rerouted off-site to be cooled and recycled back to the reactor jacket feed
stream.
The temperature of the outlet stream for the reactor jacket (CW-02) is monitored
by the controller (TIC-1B). The temperature of the reactor outlet stream is monitored using (TIC-
2). If the temperature of the reactor becomes highly elevated a signal is sent to the control valve
(V-09) to be closed. Since temperature is directly related to pressure, to avoid
the likelihood of an explosion flow into or out of the reactor is halted until de-pressurizing can
occur. Now we will discuss controlling the pressure associated with the reactor. The pressure
controlling indicator (PIC-3), is located on the reactor bed. Since the operating pressure of the
bed is 40 bars, PIC-3 is used to control and maintain this pressure, if the
pressures increase beyond that of 40 bars a signal is sent to the automated relief valve (RV-01) to
left and de-pressurized the vessel.
The pressure of the reactor outlet stream is monitored using (PIC-2). If the pressure of the reactor
becomes highly elevated a signal is sent to the control valve (V-09) to be closed. Since
temperature is directly related to pressure, to avoid the likelihood of an explosion flow into or
out of the reactor is halted until de-pressurizing can occur. Continuous monitoring of the
of reactor inlet stream (S1) pressure is done with the use of a pressure control indicator (PIC-
1). If the pressure of the stream (S1) increases, the manual gate valve (V-10) can be opened to
de-pressurized the line.

CONTROL STRATEGY (Czarina)

Refer to Visio file “Absorber”

Control Strategy for Absorber was designed to maintain satisfactory CO2 removal and to avoid
any disturbances that may lead to deviations in Operating Conditions that can have undesirable
effects. Control variables considered were flow rate of the Liquid and Liquid Temperature.
Control of Liquid Flow rate directly affects percentage of CO2 removal. As flow rate increases
percent of CO2 removal increases and vice versa for a decrease in flow rate. As such, to maintain
optimum performance of this equipment control of flow is apropos. This control can also be
employed in the incident that required amount of CO2 removal may need to be modified. Liquid
temperature must be maintained at operating conditions as deviations may lead to reverse
reactions.
The flow rate of liquid is controlled and manipulated by FIC-2. This controller monitors and
manipulates V-8 to maintain set point entered into control system. V-8 is opened/closed in
accordance to set point to maintain adequate flow. Liquid Temperature is controlled by TIC-
10. This controller is connected to E-4 which cools the Lean Amine Stream. Temperature is
monitored and maintained by adjusting the operating parameters of the E-4.

(Ref. Bedelbayev, A., Lie, B., & Greer, T. (n.d.). MODEL BASED CONTROL OF
ABSORPTION FOR CO2 CAPTURING. Retrieved
from https://pdfs.semanticscholar.org/3e9f/6e4759e78589887d37ac384864e384d4bffc.pdf)

Control Strategies (Rachel)

Refer to Visio file “Rachel distillation Column”

The distillation process is susceptible to system failures. In fact, the main priority of a chemical
plant is to ensure safe operation of the process since a potential disaster could lead to major
negative repercussions. In an effort to address this pertinent issue, instruments such as pressure
indicators and flow meters, are provided in order to carefully monitor the critical process variables
such as pressure, flow and temperature, during the plant operation. The close monitoring ensures
that the process variables are operating within the safe operating limits. In fact, these instruments
are also fitted with automatic alarm systems in an effort to alert the operators once any variation
from design occurs in the event that a critical or hazardous situation arises.

On the main feed line, the valves (V-101) and (V-104) are placed before and after the pump (P-
101) respectively in order to facilitate priming of the pump. Priming is essential as it ensures that
the pump casing is filled with liquid before the pump is started. If it doesn’t take place, the pump
casing would become filled with gases and the pump impeller would become gas-bound and would
be incapable of pumping.
The check valve (V-103) placed after the pump (P-101) is strategically placed in order to ensure
the flow of the feed is in one direction that opposes back flow which can cause cavitation in the
pump. Cavitation can degrade the performance of the pump and can cause fluctuating flow rate
and discharge pressure. The relief valve (V-102) was placed before the pump (P-101) in order to
ensure that no pressure builds up in the pipeline which can cause the pipeline to rupture. The
bypass line contains the pump (P-102) and is placed to ensure the constant feed flow in the event
that any failure in the main line occurs whether it is a leaking valve or pipeline or failure in the
main pump (P-101).

On the main feed line, there are pressure indicator and transmitter controller (PIC01 and PT01)
located between the valves (V-103) and (V-104) in order to monitor the pressure in the line to
ensure it is within the safe operating limit. There is also a feed transmitter and controller (FT and
FC) which would control the valve (V-109) to ensure the flow rate into the distillation column is
operating according to design.

For the Distillation Column (D-101), the pressure relief valve (V-131) is strategically placed in
order to protect the vessel from being susceptible to pressures exceeding the specified design
limits. When the set pressure is exceeded, the relief valve becomes that path of least resistance and
this forces the valve to open and a portion of the fluid is diverted through another route.

The distillate or overhead product of the column (D-101), enters a total condenser unit (C-101)
where the valves (V1) and (V2) are placed to control the flow of refrigerant in and out of the
condenser. These valves are highly dependent on the temperature being returned into the column.
As a result, the temperature controller (TIC02) is placed so that if the temperature is too high, the
valve (V1) would be opened to cool the condensate leaving the condenser unit but if the
temperature is too low, the valve (V1) would be closed to aid in the increase of the temperature. If
further temperature increase is required immediately, the valve (V2) would be opened at an
appropriate opening percentage to remove refrigerant and thus increase the temperature to a greater
extent.

The condensate stream leaving the condenser unit then enters the reflux drum (RD-101) where the
level controller, indicator and transmitter (LT1, LI1 and LC1) ensures that the level in the reflux
drum is maintained within the safe operating limits. If a high-level alarm (LA1) is triggered, the
level controller would open the valve (V-121) in an effort to send the reflux back into the column.
If further level decrease is required immediately, the valve (V-110) which controls the flow of the
condensate into the reflux drum, would be closed at an appropriate closing percentage. If the level
is too low, the low level alarm would be triggered which would close the valve (V-121). In the
event that the valve (V-121) fails, the valves (V-122 and V-120) are strategically placed to prevent
any potential disasters.

On the main distillate line, the valves (V-111) and (V-114) are placed before and after the pump
(P-103) respectively in order to facilitate priming of the pump. The check valve (V-113) placed
after the pump (P-103) is strategically placed in order to ensure the flow of the distillate is in one
direction that opposes back flow. The relief valve (V-112) was placed before the pump (P-103) in
order to ensure that no pressure builds up in the pipeline.

On the main distillate line, there are pressure indicator and transmitter controller (PIC03 and PT03)
located between the valves (V-113) and (V-114) in order to monitor the pressure in the line to
ensure it is within the safe operating limit. These pressure controllers would then either open or
close the valve (V-119) where the desired product propylene leaves as the distillate product. The
bypass line contains the pump (P-104) and is placed to ensure the constant distillate flow in the
event that any failure in the main line occurs whether it is a leaking valve or pipeline or failure in
the main pump (P-103).

The bottoms product of the distillation column is then sent to the reboiler unit (R-101). The valves
(V4) and (V3) are placed to control the flow of steam in and out of the reboiler. These valves are
highly dependent on the temperature of the column. As a result, the temperature controller (TC01)
is placed so that if the temperature is too high, the valve (V4) would be closed but if the temperature
is too low, the valve (V4) would be opened to aid in the increase of the temperature using steam.
If further temperature increase is required immediately, the valve (V3) would be closed at an
appropriate closing percentage to prevent the steam from leaving and thus increase the temperature
to a greater extent.

On the main bottoms line, the valves (V-123) and (V-126) are placed before and after the pump
(P-105) respectively in order to facilitate priming of the pump. The check valve (V-125) placed
after the pump (P-105) is strategically placed in order to ensure the flow of the bottoms is in one
direction that opposes back flow. The relief valve (V-124) was placed before the pump (P-105) in
order to ensure that no pressure builds up in the pipeline.
On the main bottoms line, there are pressure indicator controller (PIC05) located between the
valves (V-125) and (V-126) in order to monitor the pressure in the line to ensure it is within the
safe operating limit. These pressure controllers would then either open or close the valve (V-126)
where propane, butene and pentene leaves as the bottoms product. The bypass line contains the
pump (P-106) and is placed to ensure the constant bottoms flow in the event that any failure in the
main line occurs whether it is a leaking valve or pipeline or failure in the main pump (P-105).

REFERENCES

APV. (2008). Distillation Handbook. Available:

http://www.scribd.com/doc/64928779/Distillation-Handbook-10004-01-08-2008-US.

The Distillation Group, Inc. (2002). Distillation. Available:

http://www.distillationgroup.com/distill.htm.

R.K. Sinnott (2005). Coulson & Richardson's chemical engineering. Vol.6, Chemical
engineering design. 4th ed. Oxford: Butterworth-Heinemann.

CONTROL STRATEGIES (Andrea)

See Visio file “Andrea distillation”

As in every process, we would encounter deviations and unforeseen situations. In this case we
would look at various precautions we can take in order to prevent hazards and accidents form
happening in the industry. The de-methanizer is no exception when comes to unexpected
situations. We look at control strategies which would prevent hazards.

Firstly, we look at the feed line where we have a pump (P-301) to increase pressure in the line.
Valves V-301 and V-304 are placed before and after the pump for priming purposes. This would
help prevent cavitation, pump dry out, suction problems at startup etc. in the pump. These values
can be turned off in the event of any leakages occurring in the line. Therefore, if the main line
breaks or the pump shuts down, a bypass time is in place to pick up the flow of the feed line. On
the feed line we have a flow transmitter and controller (FT and FC), this would regulate the flow
into the distillation Column by controlling valve V-309. Pressure indicators and controllers
(PT01 and PI01) would read the pressures in the line. Bleed values are placed in front of the
pump in case of a high pressure build up in the line. These would open to prevent rupture of
pipeline.

Upon entering the distillation column, (D-301), a pressure relief valve is placed on the vessel in
case of a pressure build up within the system. If the pressure goes above what the column is
design for, valve V-331 would open.

The top’s product of the distillation column would go to the condenser unit. Where valves V1
and V2 would control the flow of the refrigerant in and out of the Condenser unit. Temperature
controller, TIC01 would monitor the temperature going back into the column, if the temperature
is too high it would open V1 to cool the condensate coming out of condenser and if the
temperature is too low, V1 would close to allow the temperature to rise. As the flow from
condenser would enter a reflux vessel, here we have a pressure indicator (PI07) and pressure
controller (PC07) would monitor the build-up of pressure in the vessel. This would be the
methane gas coming out of the condenser. These controllers would open or close V-319 sending
the methane gas to an off-gas power generation plant. For the liquid reflux we have our liquid
Controls (LT1 and LIC1) monitoring the level of the reflux vessel. When the level alarm (LA1)
reads a high level, the controls would open V-321 sending reflux back into the column and the
opposite would be done for the low level; the controls would close V-321. The condensate main
line inlet includes pump, P-303. A bypass line is installed in case of any unpredicted situations
that may occur in the main line. Valve V-322 and V-320 are placed as back up vales incase V-
321 fails, it would be able to close.

The bottom’s product would be sent to the reboiler (R-301) here is steam and condensate is
control by V3 and V3 in and from the reboiler. A temperature indicator, (TI2) would indicate the
temperature of bottom tray temperature. A bypass line was also added into the reboiler stream for
any unpredicted situation.

REFERENCES

APV. (2008). Distillation Handbook. Available:

http://www.scribd.com/doc/64928779/Distillation-Handbook-10004-01-08-2008-US.
The Distillation Group, Inc. (2002). Distillation. Available:
http://www.distillationgroup.com/distill.htm.

R.K. Sinnott (2005). Coulson & Richardson's chemical engineering. Vol.6, Chemical
engineering design. 4th ed. Oxford: Butterworth-Heinemann.
 P&ID’s
REACTOR P&ID (JILLIAN)
Flow meter
F-02 S2
CV-03
F
AI-2 CV-02
P-02

V-09

PIC-2 TIC-2 Relief valve

RV-01

PIC-3

FIC-1

V-06
TIC-1A
Strainer 2 TIC-1B

CW-01
CW-02
V-07 V-05
V-08

V-04

Flow meter
F-01 TI-1 CV-01
F V-03
V-02
E-01 V-10
TT-2
AI-1
Strainer 1
FIC-2
PIC-1

V-01
P-01

S1
ABSORPTION COLUMN P&ID (Czarina)
 DE-PROPANIZER P&ID (Rachel)

Refrigerant in

V1

V-110
C-101

LA1
Reflux Drum
RD-101 LI1
V2 LT1

PIC03
Refrigerant out
PT03

LC1
P-21

V113 V114
TIC-02 V-111
V112 P103 PIC04

PT04

P-26
V117 V118
P-28
V115
V-109
V116 P104 Tops product
FC
V122 V121 V120 V119

FT
D-101
PIC01 TI-01 TT-01

PT01

Feed P-3
TC-01

V-103 V-104
V-101
P-101 PIC02
Bottoms
V-102
PT02 PIC05

P-8
P-60
V-107 V-108 V-125 V-126
V-105 Condensate
P-102 V-123
V-124 P-105

V-106 V3 PIC06
P-69

V-131 V-129 V-130

Steam in V-127
V4 P-106
V-128
R-101
 De-methanizer P&ID (Andrea)

Refringent out Tops-product

V1
V-319
V-310 PC07

C-301
PI07

Reflux Column
V2 LT1 LA1

PI3
Refringent out
LIC1 V-313
V-311 P-21
PT3

V-312 V-314
TIC01 P-303
PI4

PT4
V-315 P-26

V-317 V-318
V-309
V-316 P-304
FC
V-322 V-321 V-320
PI0
1
PT0
1
FT
D-301 TI02 TT02
Feed
P-3

V-303 V-304 TC02

V-301 PI-05
P-301
V-302
P-60
V-325 V-326
PI02
V-323
P-305
PT02 V-324
PC06
P-8

V-307 V-308 PI06

Bottoms
V-305
P-302 P-69

V-329 V-330
Steam in R-301 V-327
V-306 V-331 V4 P-306
V-328

V3
Condensate
 HAZOP

13.1 HAZOP Analysis of Methanol to Olefins (MTO) Reactor

(Jillian)

The MTO reactor converts methanol to olefins using a diluted methanol feed stream and H-SAPO-34 zeolite type catalyst. The
operating temperature of the reactor is 400 o C and operating pressure is 40 bars, which makes this reactor a high-pressure vessel. The
products formed are is very flammable and explosive, therefore if proper care and precaution are not taken an explosion can occur.

DEVIATIONS
(GUIDE PROPERTY POSSIBLE CAUSES POSSIBLE CONSEQUENCES RECOMMENDATIONS
WORDS)

COMBINED FEED TO THE REACTOR (R-100)

No Methanol Inlet  Control valve  Technological Problem.  Install CH3OH

Concentration (V-01) failure. Methanol Conversion is 0. flowmeter (F-01) and
indicator (FIC-2).
 Install a secondary
emergency relief valve.
More Methanol Inlet  Control valve  Thermal runaway effect  Add Water to the inlet
Concentration (V-01) failed to (Reactor Temperature (S1) of the reactor to
close. Increase) and possible improve selectivity.
explosion.
Less Methanol Inlet  Control valve  Technological Problem and  Install a CH3OH flow
Concentration (V-01) failed to Conversion is too low. meter (F-01).
open.
Other Than Methanol Inlet  Wrong reagent  Vessel Rupture  Review Quality and
Concentration or raw material  Formation of undesirable Assurance Procedures.
fed to S1. Products. (Do more sampling)
 Decreased conversion
As Well As Methanol Inlet  Impurities in  Technological Problem in  Review Quality and
Concentration raw material Reactor Assurance Procedures
stream (S1).
No Methanol Inlet  Methanol  Technological Problem and  Install Methanol
Concentration pipeline (S1) conversion is zero. flowmeter (F-01) &
may be clogged. composition indicator
 Control valve (AI-1).
(V-01) failure.
More Methanol Inlet  Control valve  A very high wt. % of methanol  Add water to the inlet
Concentration (V-01) failed to may form explosive mixtures. (S1) of the reactor to
close.  Low selectivity. improve selectivity.
No Flow  Flow Controller  Loss of feed to reaction section  Ensure there is good
(FIC-2) failure. and no output communication with
 Line (S1) raw materials storage
fracture. operator.
 Line (S1)  Install low flow alarm.
blockage.  Check design of pump
strainer (Strainer 1).

More Flow  Flow Controller  Decreased CH3OH  Install high flow alarm
(FIC-2) failed to Conversion.
close.  High concentrations of
methanol leading to explosive
mixtures.
Less Flow  Flow Controller  Less CH3OH Conversion.  Install low flow alarm
(FIC-2) failed to
open
As Well As Flow  Water  Out of spec. supply  Review Quality and
Contamination Assurance Procedures
 Impurities
Other Than Flow  Wrong Feed  Decreased conversion.  Review Quality and
Delivered  Increased formation of Assurance Procedures
undesirable products
Reverse Flow  Pump (P-01)  This may form explosive  Install check valve
failure, non- mixtures since olefins are (CV-01) at pump
return valve flammable and explosive. discharge.
failure,  Install high level alarm
 Over- shutoff at feed.
pressurisation of
reactor.
More Temperature  Temperature  CH3OH Conversion.  Adjust cooling stream
Transmitter concentrations increase and flow rate of reactor bed
(TT-2) failure. forms potential explosive (V-07) to control
 External Fire. mixture of hydrocarbons. temperature.
 Decreased conversion and  Install a high
selectivity. temperature alarm.
 Increased Reaction  Install gas flowmeters
Temperature leading to (F-01) or sensors.
runaway effect.  Improve on fire
protection services and
mechanisms.
Less Temperature  Temperature  Decreased Selectivity.  Install a low
Controller (TIC-  Low Pressure. temperature alarm.
3A) Failure

COOLING (COOLANT) STREAM PASSING THROUGH REACTOR (R-100)

Higher Inlet and Outlet  Cooling water  Thermal runaway effect and  Install high temperature
Temperature valves (V-04, possible explosion alarm
05, 06)
malfunction or
failure.
Lower Inlet and Outlet  Control valve  The temperature of the reactor  Install low temperature
Temperature (CV-03) failure, may become very cool alarm
operator fails to
act on hearing
alarm
No Flow  Cooling water  Runaway effect and possible  Install high temperature
valves (V-04, explosion alarm.
05, 06) or flow  Install cooling water
controller flowmeter and low flow
malfunction. alarm.
  Cooling water  Select valve to fail-
service failure. open.
 Check and monitor
reliability of water
service.
 Install filter (Strainer 2)
with maintenance
procedures.
More Flow  Control valve  The reactor becomes very cool  Install low temperature
(V-07) failure, and reactant concentration alarm.
operator fails to builds up and potential  Instruct operators and
act on hearing runaway effect on heating. update safety
alarm. procedures.
Less Flow  Pipe (CW-01)  Temperature of process fluid  High Temperature
Leakage. remains constant or increases Alarm.
 Temporary  Thermal runaway effect  Install cooling water
Water Source flow controller (FIC-1)
Failure. and low flow alarm.
 Partially  Check and monitor
clogged cooling reliability of water
line (CW-01). service.
  Install filters with
maintenance (Strainer
2) procedures.

Part of Flow  Partially  Less Cooling, Potential  Install filters (Strainer

clogged cooling runaway effect. 2) with maintenance
line (CW-01). procedures.
Reverse Flow  Failure of water  Less cooling, runaway effect  Install check (CV-03)
source or high and explosion or non-return valve.
backpressure
resulting in
backward flow

REACTOR PRODUCTS LEAVING THE REACTOR (R-100)

More Temperature  Temperature  Product concentrations  Install a high
Controller (TIC- increases and forms potential temperature alarm.
2) Failure. explosive mixture.  Install gas flowmeter
 External Fire.  Increased Product Temperature (F-02) or sensors.
 High Reaction leading to runaway effect.  Improve on fire
Temperature protection services and
(TT-4). mechanisms.
Less Temperature  Temperature  Low Reactor Pressure.  Install a low
Controller (TIC- temperature alarm.
2) Failure
No Flow  Flow Controller  No production of ethylene &  Install low flow alarm.
failure. propylene.  Check design of pump
 Line fracture strainers (Strainer 1).
(S2).  Ensure catalyst
 Full Line (S2) regeneration schedule is
blockage. adhered to.
 Wrong Catalyst
or Catalyst is
fully consumed.
Less Flow  Feed Flow  Less production of ethylene &  Install low flow alarm
Controller (FIC- propylene.
2) failed to open
As Well As Flow  Water  Out of spec. supply to the  Review Quality and
Contamination reactor. Assurance Procedures.
 Impurities
Other Than Flow  Wrong Feed  Decreased ethylene &  Review Quality and
Delivered to the propylene production. Assurance Procedures.
Reactor  Stream may contain many
undesirable products.
Reverse Flow  Pump failure,  This may form explosive  Install check valve at
non-return valve mixtures. pump discharge (CV-
(CV-2) failure, 03).
 Over-  Install high level alarm
pressurisation of shutoff at feed.
reactor.

OPERATING CONDITIONS OF REACTOR (R-100)

More Reactor Pressure  Relief valve  Reduced Yield.  Install vessel refractory
(RV-01) fails  Formation of undesirable to reduce temperature
closed. products. gradient and hot spots.
 Development of Temperature  Install pressure
Gradients with localized hot indicators (PIC-3) the
spots leading to impairment of reactor bed.
the catalyst to produce high  Install high pressure
selectivity of olefins. alarm for dangerous
 Vessel overpressure or rupture. build-ups and initiate
emergency shutdown
procedures.
Less Reactor Pressure  Release (RV-  Decreased Conversion.  Install pressure
01) fails open. indicators at inlet (PIC-
 1)and outlet (PIC-2) of
the reactor.
 Consider detection and
emergency planning.
More Temperature  Temperature  CH4 concentrations within the  Adjust cooling stream
Controller (TIC- bed increases and forms flow rate (CW-01).
3) Failure. potential explosive mixture of  Install a high
 External Fire. hydrocarbons. temperature alarm.
 Decreased conversion and  Install gas flowmeters
selectivity. or sensors.
 Increased Reaction  Improve on fire
Temperature leading to protection services and
runaway effect. mechanisms.
Less Temperature  Temperature  Decreased Selectivity.  Install a low
Controller (TIC-  Low Pressure. temperature alarm
3) Failure
 13.2 HAZOP performed on Absorber unit (czarina)
POSSIBLE
DEVIATION PROPERTY POSSIBLE CAUSES RECOMMENDATIONS
CONSEQUENCES

FEED STREAM TO ABSORBER (P-9 AND P-2)

Less Flow  Pump (E-3)  Decrease in  Install backup

Malfunction pressure in E-1 pump

Less Flow  Blockage in P-9  Decrease in  Shut off V-1 and

pressure in E-1 V-2 and open V-3
to redirect flow

More Flow  Surge in flow in  Increase in of  FIC-7 adjusts V-2

P-9 Pressure in E-1

 Less Absorption

More Flow  Malfunction of  Increase in of  FIC-7 adjusts V-2

FIC-7 Pressure in E-1

 Less Absorption

No Flow  Malfunction of  Decrease in  Shut off V-1 and

FIC-7 pressure in E-1 V-2 and open V-3
to redirect flow
  Lean solvent
exiting at P-12

 No CO2 Removal

No Flow  Blockage in P-9  Decrease in  Shut off V-1 and

pressure in E-1 V-2 and open V-3
to redirect flow
 Lean solvent
exiting at P-12

 No CO2 Removal

Low Pressure  Low Flow from  Decrease in  Install PIC on P-9

E-3 pressure in E-1 controlling E-3 to
increase flow

High Pressure  High flow from  Increase in of  Install PIC on P-9

E-3 Pressure in E-1 controlling E-3 to
decrease flow
 13.3 HAZOP Performed on the De-Propanizer Column
(Rachel)

Node Guide Deviation Cause Consequences Existing Safeguards Action Required

Word
Feed Pump Low Low Flow 1. Leaking feed Pump (P-101) failure Flow indicators and Conduct routine checks on
(P-101) valve V-101 controllers (FC and FT) instrumentation and
2. Leaking relief Release of hazardous are placed to detect any equipment should be made by
valve V-102 substances into deviation from safe the field operator
3. Leak in atmosphere operating flow
pipeline

High High Flow 1. Pump (P- Relief valve (V-102) Bypass feed line with Operators must revise
101) opens and releases pump (P-102) is used in Standard Operating
experiences hazardous substances operation instead Procedures (SOPs)
increased into atmosphere
pumping Conduct routine maintenance
capacity on equipment
2. Negligence of
operators
 No No Flow 1. V-101 fails Cavitation in pump (P- Bypass feed line with Place a fail open valve
shut 101) pump (P-102) is used in
2. Blockage operation instead Conduct routine maintenance
occurs in the on equipment
pipeline Test the flow before startup
3. FT and FC
indicates false Install remotely activated
readings block valves at feed tanks to
4. Catastrophic allow operators to stop flow
failure of pipe

Low Low Pressure 1. Leaking relief Hazardous substances Bypass feed line with Conduct routine maintenance
valve V-102 released into pump (P-102) is used in on equipment
atmosphere operation instead
High High 1. Relief valve Rupture of pipeline Bypass feed line with Conduct routine maintenance
Pressure V-102 fails pump (P-102) is used in on equipment
shut P-101 failure operation instead

Distillation Low Low 1. Failure to Product quality The temperature Operators must revise
Column Temperature open V4 diminished due to controller (TIC01) is Standard Operating
(D-101) steam inlet ineffective separation placed to indicate Procedures (SOPs)
valve to the whether an undesired
 reboiler (R- temperature is detected Conduct routine checks on
101) and control the valve V4 instrumentation and
2. Steam leakage equipment should be made by
of the V3 the field operator
steam outlet
valve out of
the reboiler
(R-101)
High High 1. Increased Flooding in the column The temperature Operators must revise
Temperature steam flow may occur due to controller (TIC01) is Standard Operating
via V4 steam excessive vapor flow placed to indicate Procedures (SOPs)
inlet valve to whether an undesired
the reboiler Product quality is temperature is detected Conduct routine checks on
(R-101) affected and control the valve V4 instrumentation and
2. Refrigerant equipment should be made by
temperature The temperature the field operator
too high and controller (TIC02) is
is not in placed to indicate
compliance whether an undesired
with design temperature is detected
and control the valve V1
Low Low Pressure 1. Failure to Low efficiency of The temperature Install pressure indicators and
open V4 separation leading to controller (TIC01) is controllers
steam inlet inadequate liquid hold- placed to indicate
valve to the up due to decreased whether an undesired Install low pressure alarm
reboiler (R- vapor flow temperature is detected
101). This and control the valve V4 Conduct routine checks on
means less Loss of desired product instrumentation and
vapor enters equipment should be made by
column the field operator

High High 1. Increased Rupture of column The pressure relief valve Install pressure indicators and
Pressure steam flow (V-131) is placed in controllers
via V4 steam Loss of desired product order to protect the vessel
inlet valve to from being susceptible to Install high pressure alarm
the reboiler pressures exceeding the
(R-101) specified design limits Conduct routine checks on
causing an instrumentation and
increased equipment should be made by
vapor flow the field operator
into the
column and
 pressure
buildup
Low Low Flow 1. Pump (P-101) Column dry out There is also a feed Install low level alarm
failure transmitter and controller
2. Pipe blockage Product quality is (FT and FC) which Conduct routine checks on
3. Valve (V- affected would control the valve instrumentation and
109) fails (V-109) to ensure the equipment should be made by
4. Leakage in flow rate into the the field operator
pipeline distillation column is
operating according to Make a bypass
design
High High Flow 3. Pump (P- Relief valve (V-102) Bypass feed line with Operators must revise
101) opens and releases pump (P-102) is used in Standard Operating
experiences hazardous substances operation instead Procedures (SOPs)
increased into atmosphere
pumping Conduct routine maintenance
capacity on equipment
4. Negligence of
operators
No No Flow 1. V-101 fails Column dry out Bypass feed line with Install low level alarm
shut pump (P-102) is used in
No operation occurs operation instead
 2. Blockage Conduct routine maintenance
occurs in the on equipment
pipeline
3. FT and FC
indicates false
readings
4. Catastrophic
failure of pipe

Condenser High High 1. Refrigerant Incomplete phase The temperature Reduce the temperature of the
(C-101) Temperature temperature change controller (TIC02) is refrigerant
too high and placed to indicate
is not in whether an undesired Operators must revise
compliance temperature is detected Standard Operating
with design Procedures (SOPs)

Low Low 1. The Phase change affected The temperature Operators must revise
Temperature refrigerant controller (TIC02) is Standard Operating
flow rate is placed to indicate Procedures (SOPs)
higher than whether an undesired
that in the temperature is detected Conduct routine checks on
instrumentation and
 design equipment should be made by
specifications the field operator

Reboiler High High 1. Increased Bottoms product The temperature Conduct routine checks on
(R-101) Temperature steam flow quality affected controller (TIC01) is instrumentation and
via V4 steam placed to indicate equipment should be made by
inlet valve to whether an undesired the field operator
the reboiler temperature is detected
(R-101)

Low Low 1. V4 steam inlet Low vapor rate enters The temperature Conduct routine checks on
Temperature valve to the column controller (TIC01) is instrumentation and
reboiler (R- placed to indicate equipment should be made by
101) fails Phase change affected whether an undesired the field operator
close temperature is detected
2. Leakage
occurs in the
steam line
Reflux High High Level 1. Flow of Higher amounts of The level controller and Conduct routine checks on
Drum condensate reflux which deviate transmitter (LT1 and instrumentation and
into the drum from design, would be LIC1) ensures that the
 is too high returned into the level in the reflux drum equipment should be made by
and is not in column is maintained within the the field operator
compliance safe operating limits
with design
If a high-level alarm
(LA1) is triggered, the
level controller would
open the valve (V-121) in
an effort to send the
reflux back into the
column
Low Low Level 1. Failure of the Poor liquid level The level controller and Conduct routine checks on
opening of indication can cause transmitter (LT1 and instrumentation and
valve (V-110) expensive operating LIC1) ensures that the equipment should be made by
which problems and product level in the reflux drum the field operator
controls the degradation is maintained within the
flow of the safe operating limits
condensate
into the reflux If the level is too low, the
drum low level alarm would be
triggered which would
close the valve (V-121)
 13.4 Hazop on De-Methanizer Column

(Andrea)

Study Process Guide Causes Consequences Action

node parameters word
Equipment: Distillation Column ,D-301
Distillation Temperature Low Less flow in D-301 Ineffective separating process Install temperature
Column Loss of heating from R- Pressure change indicators.
301
Temperature indicator TI- Loss of product. Instruct operators on
02 fails procedure.

Isolation upgrade.
Attention to heat input and
output controls
 High High pressure in D-301 Separation can’t be done Install temperature
indicators
Valve V1 fail. Phase change effect
Educate operators on
Reboiler control TC-02 Pressure change procedure
failure
Film boiling in column and Attention to heat input and
Heating medium inside R- reboiler output controls
301 leak into process
Change in product quality
Pressure Low Valve V-331 leakage Low efficiency of separation Install pressure indicators

Loss of product

Pressure high Pressure indicator Rupture of column Instill high pressure alarm

Pressure controller fail Product loss Instill pressure relief valve

Vapour pressure high Low efficiency of separation

Flow No Valve V-309 fails Column dry out Schedule maintenance
procedure
Tube leakage and No operation
blockage Commence bypass inline
into operation
Pipe blockage
Install low level alarm
Control valve shut
Emergency plant shutdown
Pump failure P-301
less Pipe blockage Column dry out Install low level alarm

Control valve, V-309 shut Change in product quality Schedule maintenance

procedure
Pump, P-301 fails
Make bypass
Tube leakage
 high Control valve, V-309 fully Flooding in column Instill high level alarm
open
Change in product quality Schedule maintenance
Increase pump capacity procedure
Temperature decrease
Control valve V-309 fails Install control valve
Rise in bottom liquid level
Install flow indicator
Equipment: Condenser, C-301
Condenser Temperature high Fouling on tube or shell Incomplete change to the Maintenance of equipment
side desired phase

Temperature of refrigerant Incomplete change to the Reduce refrigerant

higher than that of the desired phase temperature or increase
design flow rate

Low Refrigerant rate Incomplete change to the Increase refrigerant flow

desired phase rate
 Refrigerant side fouling or Incomplete heat transfer Cleaning tubes
blockage

Refrigerant flow rate Incomplete heat transfer Install flow indicator

increase
Install control valve
Poor vacuum Incomplete heat transfer Maintenance of tubes in
condenser
Phase change affected
Cooling water flow
increase
Contamination Of Leakage of tubes and Contamination of process fluid Proper maintenance and
process refrigerant into process operator alert
line line
Equipment: reboiler, R-301
Reboiler Level Low High flow rate of bottom Burning out heating element Install a level indicator and
product existing alarm

Low flow entering the

column
High Poor circulation of liquid Incomplete heat transfer Regular maintenance of
in reboiler equipment
 Phase change affected

Temperature Low Valve V4 fails Low heat transfer Open steam valve, V4, so
reboiler heats up
Temperature transmitter Phase Change affected
TT02 stops working Regular maintenance of
Low vapour rate going back equipment
Scaling in tubes of into the column
equipment
Purities of Components
Leakage in steam line changes
High Steam valve, V4 fails Flash vaporization Regular maintenance of
equipment
Bottoms product purity is
affected
Contamination Of Leakage of tube and Unwanted reactions Proper maintenance and
process streams goes in operator alert
fluid Contamination of process fluid
Equipment: Pumps using pump on feed line as example
Pump Flow Low Leakage in feed pipe line Release to atmosphere Regular maintenance of
equipment
V-301 fails Economic loss
 Install gas detectors
Relief valve, V-302 is
open Commence bypass line into
operations
high Pump, P-301 fail on Release to environment by Monitor equipment
relief valve, V-302
Overfilling- human error
No Blockage in pipe line Cavitation of pump Install flow meters in line

V-301 close/jammed Pump dry out Check valves to ensure that

they are open
Suction Vessel empty Damage of equipment
Pressure Low Relief valve V-302 is Release to environment Install pressure indicators
open
Rupture of pipeline Maintenance of equipment
Feed line rupture
Close V-304
Blockage of feed pipeline
Commence bypass line into
operation
High Relief valve V-302 fail Vessel over pressure/ rupture Install pressure indicators
and controls
Close valve V-308

Commence bypass line into

operation
 HEALTH, SAFETY AND ENVIRONMENT (HSE)

HEALTH, SAFETY AND ENVIRONMENT (Jillian)

Processes HSE Comparison:

HSE for Process Components:

Methanol-

Chemical Toxicity- According to the World Health Organization (1997), “Methanol is

irritating to the eyes, skin and respiratory tract. A broad range of ocular effects was found
to have been associated with longer-term occupational exposure to lower levels of
methanol. Severe oral and inhalation exposures have resulted in central nervous system
depression, blindness, coma and death. The toxic dose is a prominent variable feature in
the toxicity of methanol. The symptoms of methanol poisoning, which may not appear
for 12 to 24 hours include, nausea, abdominal pain, weakness, dizziness, and lack of
consciousness ranging from coma to colonic seizures”. Individuals who work in methanol
industries may be chronically exposed therefore; Occupation Health and Safety Act
(OSHA) regulatory concentration of methanol enforced to protect workers from
potentially harmful exposure without adverse effects in an 8-hour day is 260 mg/m3 or
200 ppm. (NIOSH, 1976)

Environmental Concerns- Methanol is rapidly degraded in the environment with no

evidence of bioaccumulation. The available data do not suggest that there are any
significant effects in the environment (Howard et al., 1992). It is harmless at natural
amounts due to how quickly it biodegrades. Hence methanol does not pose a significant
hazard for either aquatic or terrestrial life, except in the case of a spillage. Therefore,
extra care must be given when handling.
 Health and Safety Considerations-There should be no sources of ignition in the vicinity of
methanol storage or use. Methanol should be stored in a cool closed system away from
direct sunlight and moisture, with adequate ventilation and explosion-proof electrical
equipment and lighting. Methanol is extremely flammable, because of this its storage tanks
should be surrounded by a dike and protected by a carbon dioxide foam-type fire-
extinguishing system. For relatively small Spillages measuring less than twenty-five (25)
liters, are considered relatively small and can be absorbed onto sand or vermiculite.

The following Personal Protective Equipment should be worn when handling Methanol:

 Fire resistant clothing (FRC).

 Chemical suit for handling
 Safety gloves
 Goggles
 Breathing air
 Most importantly, ensure vapor concentrations are below the occupational
exposure limit.

Methane-

Chemical Toxicity- Methane gas is relatively non-toxic, therefore there is no OSHA PEL
Standard attached to this compound. Its health effects are associated with being a simple
asphyxiant, thereby displacing oxygen from the lungs. Methane is extremely flammable
and prone to explosions at concentrations between 5% to 15%, which are the lower
explosive limit and upper explosive limit, respectively. At concentrations of about 9%
methane, the most violent explosions have been reported to have occurred.

Environmental Concerns- When compared to other volatile organic compounds (VOCs)

methane does not donate significantly to photochemical smog and the formation of
ground level ozone. The main impact of methane is its high global warming potential as a
 greenhouse gas, although the levels of methane in the environment are fairly low it is
ranked amongst the worst of the greenhouse gases.

Health and Safety Considerations-At low concentrations methane gas is considered to be

harmless. However, at high concentrations methane gas displaces oxygen from air
making it difficult to breathe, leading to asphixicer, increased heart rate, dizziness and
Methane is considered to be extremely flammable and can become explosive under
pressure when heated. There should be no sources of ignition in the vicinity of methane
storage or use.

The following Personal Protective Equipment should be worn when handling Methanol:

 Eyes/Face shields
 Wear splash resistant safety goggles.
 Protective Clothing
 Wear appropriate chemical resistant gloves.
 Respiratory Equipment for frequent use or heavy exposure,

Process Pollution:

Air Pollution- Industrial plants have become necessary to help in the synthesis of
products for modern societies however the resultant waste products themselves can be harmful to
the environment. The responsibility to reduce the overall impact of gaseous and liquid effluent
from harming the environment must be addressed in the design phase of any chemical process.

Specifically, with regard olefin production using methanol as feedstock the main pollutant is
gaseous carbon dioxide. Carbon dioxide results mainly from the combustion of fossil fuels. The
gas is a main greenhouse gas and its presence in the atmosphere has been a proven contributor to
a phenomenon known as global warming. Mitigation of the hazard posed by carbon dioxide in
the atmosphere can be accomplished by using various methods and through scientific research
new methods are being discussed, however for any method to be utilized reasonable practicality
has to be achieved especially regarding cost of implementation. One such cost effective method
is the overall reduction of the process carbon footprint by planting trees. Trees through a process
called photosynthesis use carbon dioxide from the atmosphere during daylight hours and readily
assimilate it into carbohydrates, the trees during the process also release oxygen. Although at
night trees release carbon dioxide back into the atmosphere, the amount released is
approximately half the gas used during the day so there is a positive net loss of the greenhouse
gas. Another method is to synthesize methanol from the raw materials, atmospheric carbon
dioxide and hydrogen over a palladium/copper catalyst. Although this method is more expensive
than the aforementioned method it would allow the process to utilize its waste product to form
one of its raw materials. This recyclability would greatly reduce the overall carbon footprint and
thereby save the environment.

Reactor HSE

Numerous health, safety and environmental measures were put into place to minimize hazards
associated with the Fluidizing Bed Reactor (FBR). It is understood that all risk present within a
process and its equipment cannot be removed, however they can be mitigated. Since the FBR is
highly exothermic a lot of heat is released to the surroundings. To control or minimize exposer to
personnel and the environment a reinforced gunnite lining was applied internally, along with the
installation of a calcium silicate external insulation covered with a weather jacket. A barrier was
mounted around the reactor to keep unauthorized personnel out and numerous signs installed to
give proper warning for the dangers present. It is highly recommended that proper personal
protective equipment (PPE) be used if and only if remedial works are necessary to be performed
during operation. Some such PPE are heat retardant gloves, fire resistance clothing and steel toes
shoes just to name a few. It is also advised that personnel take periodic breaks while working
under those conditions and ensure they are properly hydrated. Since the FBR is a high-pressured
vessel, it falls under the API510 code which is the most utilized vessel code used locally. In
accordance with API510 external visual inspection is to be conducted every five (5) years and
internal visual inspection every ten (10) years. Operations are responsible for the up keep and
scheduling of the maintenance works. In case of upset conditions or emergencies an alarm is
installed on the reactor which is triggered at elevated conditions. In that instance the control
valves present within the inlet and outlet of the reactor are closed, followed by de-pressurizing of
the vessel.

References

Howard et al., 1992. Handbook of Environmental Degradation Rates. Chelsea, MI: Lewis
Publishers.

World Health Organization, Geneva (1997), Methanol Health and Safety Guide.

Carbon Dioxide (CO2) (Czarina)

Inhalation of CO2 is not harmful to health at low concentrations. As concentration increases,
persons may experience the symptoms such as dizziness, confusion, and loss of consciousness.
At high concentration that may be present in confined spaces, inhalation of CO2 may lead to
fatalities from asphyxiation.
CO2 is classified as a ‘substance hazardous to heath’ under the control of Substances to Health
Regulations 2002(COSHH) when in concentrations of 500 ppm and 15000ppm. Exposure Limits
for CO2 are as follows:
 Long-term exposure limit (8- hr reference period)- 5000 ppm
 Short-Term Exposure limit (15min reference period) – 150000 ppm.
In the case of leak of spill evacuate all non-essential personnel and ventilate area. Carbon dioxide
concentration must be at a safe level before personnel may be allowed to enter. When handling
CO2 there must be adequate ventilation, inhalation must be avoided, and work should never be
done on a pressurized system. All storage containers, piping, valves and fitting used must be
designed for gaseous Carbon Dioxide.
Reference:
(n.d.). Retrieved from http://www.hse.gov.uk/carboncapture/carbondioxide.htm
Material Safety Data Sheet: Gaseous CO2. (n.d.). Retrieved from
http://www.uigi.com/MSDS_gaseous_CO2.html
 Monoethanolamine (MEA) (Czarina)
Exposure to MEA poses several hazards. Health effects of exposure are outlines below:
Inhalation:
 nasal discomfort and discharge.
 coughing and chest pain
 prolonged exposure may lead to injury of respiratory tract.
First Aid: Move to fresh air and seek medical attention.

Eye Contact:
 severe irritation, pain and discomfort, excess blinking and tear production
 redness
 swelling of conjunctiva
 burns of cornea
First Aid: Flush eyes and seek medical attention.
Skin Contact:
 pain, swelling, redness
 fissures, ulceration
 possible bleeding
 prolonged contact may result in absorption of potentially harmful amount of chemical
First Aid: Remove contaminated clothing. Use medical shower and seek immediate medical
attention.
Ingestion:
 Chemical burns to mouth, throat, esophagus and stomach
 nausea, diarrhea, dizziness drowsiness
 circulatory collapse
 coma
First Aid: Do not induce vomiting. Drink 2 glasses or milk or water and seek immediate
medical attention
Swallowing aspiration may cause lung damage and repeated exposure may lead to liver and
kidney damage. Medical conditions such as dermatitis, asthma, inflammatory or fibrotic
pulmonary disease may be aggravated by exposure.
In the case of fire, it should be extinguished with water spray or by applying alcohol-type or all-
purpose foam. In the instance of a spill the area should be evacuated and ventilated. Only trained
and properly protected personnel involved in clean-up operations.
When handling MEA, persons should avoid contact with eyes, skin, clothing, avoid breathing
vapor, avoid ingestion and wash hands after handling. MEA should be used with adequate
ventilation and appropriate PPE must be worn. (eyewear, gloves, respiratory protection)
Reference:
C. (n.d.). SAFETY DATA SHEET: MONOETHANOLAMINE(Publication).

Absorber HSE (Czarina)

Gas absorption uses chemicals such as MEA and CO2 and these should be handles as outlined in
their respective MSDS.
Personal Protective Equipment Required:
 Hardhat
 Safety Glasses or goggles
 Closed-toe shoes
 Long Pants
 Eye wash stations and medical shower stations are also available in the case of exposure
to any hazardous chemicals.
Warning signs are placed on all hot surfaces cautioning and indicating personnel of hot surfaces.
In the instance where an emergency shutdown is required all valves allowing flow into the
absorber are shut off and power is disconnected. Flow controllers located on the feed stream and
lean amine stream, connected to an emergency shutdown switch will shut off valves
automatically when the switch is turned on and disconnect power. If this emergency stop fails,
the system can be manually shut down by physically closing valves located on these lines.
Inspection of equipment should be done regularly to ensure equipment is functioning properly,
emergency systems are working and that the equipment is safe and doesn’t pose any other risks
or hazards other than those that are outlined.
 HSE ON COMPONENTS (Rachel)

 ETHYLENE:
 HAZARD IDENTIFICATION:

Ethylene is highly flammable and is a simple asphyxiant which results in asphyxia, caused by a
decrease in the oxygen content below that which is necessary to support life. As a result of the
oxygen deficiency, prolonged inhalation of substantial concentrations of ethylene can cause rapid
breathing, diminished mental alertness and impaired muscular co-ordination, and exhaustion.
Once asphyxiation progresses, symptoms such as nausea and unconsciousness are quite common.
Unfortunately, this decrease in oxygen content may eventually lead to death.

If ethylene, in the form of rapidly evaporating liquid makes contact with the skin, cryogenic burns
or frostbite may occur. Frostbite can also result in blistering.

 PRECAUTIONARY STATEMENTS:

It is advised that ethylene is kept away from heat, hot surfaces, sparks and other ignition sources.
As a result of this, smoking is strictly prohibited. It is also advised that the gas should not be
inhaled but if it occurs, the person should be removed from the contaminated area to a fresh air
environment and medical attention sought out quickly. In terms of the storage considerations, it is
advised that ethylene is placed in a cool area with proper ventilation that is protected from the
sunlight.

 PERSONAL PROTECTIVE EQUIPMENT (PPE):

A list of the appropriate PPE is given below:

1. Safety glasses containing side shields are preferred to avoid liquid splashes, mists, gases
or dust
2. Gloves which are chemical-resistant and impervious should always be worn when handing
the chemical products
3. Nomex coveralls (Flame resistant coveralls) should be worn in an event that there is a
chemical fire
4. A thermally insulating steel toe boot which covers the ankle should be worn to prevent
harm from falling objects or compression or risk of chemical fires
 5. Industrial safety helmets to prevent harm of falling objects or bumping of head
6. Airmuffs or airplugs can be used to protect the users exposed to noise levels above 85dB
7. Respiratory protective equipment should be worn in the oxygen-deficient atmosphere

 BUTENE:
 HAZARD IDENTIFICATION:

Butene is highly flammable and is a simple asphyxiant. This suggests that inhalation of high
concentration may cause dizziness, fatigue, and nausea. Massive exposure may cause
unconsciousness and death. In addition to this, if butene, in the form of rapidly evaporating liquid,
comes into contact with the skin, it can result in cryogenic burns or frostbite.

 PRECAUTIONARY STATEMENTS:

It is advised that the gas should not be inhaled but if it occurs, the affected person should be
removed from the contaminated area to a fresh air environment and medical attention sought out
quickly. The butene storage cylinder should be stored and used in cool areas with proper ventilation
which are away from any possible sources of heat or ignition.

 PERSONAL PROTECTIVE EQUIPMENT (PPE):

A list of the appropriate PPE is given below:

1. Safety glasses containing side shields are preferred to avoid liquid splashes, mists, gases
or dust
2. Gloves which are chemical-resistant and impervious should always be worn when handing
the chemical products
3. Nomex coveralls (Flame resistant coveralls) should be worn in an event that there is a
chemical fire
4. A thermally insulating steel toe boot which covers the ankle should be worn to prevent
harm from falling objects or compression or risk of chemical fires
5. Industrial safety helmets to prevent harm of falling objects or bumping of head
6. Airmuffs or airplugs can be used to protect the users exposed to noise levels above 85dB
7. Respiratory protective equipment should be worn in the oxygen-deficient atmosphere
  PENTENE:
 HAZARD IDENTIFICATION:

Pentene is an extremely flammable in both liquid and vapor phases. Also it is poses a threat to the
aquatic life which often leads to long lasting effects. Inhalation of substantial concentrations of
pentene can dizziness, fatigue, and nausea. If ingested, a person would experience extreme forms
of nausea and vomiting.

 PRECAUTIONARY STATEMENTS:

Ensure the pentene is kept away from any possible sources of heat or ignition. Stop leaks if possible
without personal risk. For small spills it is advised that sand or other non-combustible material is
used for absorption. For large spills, place in a dike for later disposal. Ensure that the area is
cordoned off. It is also advised that pentene storage cylinder is stored in cool areas with proper
ventilation.

 PERSONAL PROTECTIVE EQUIPMENT (PPE):

A list of the appropriate PPE is given below:

1. Safety glasses containing side shields are preferred to avoid liquid splashes, mists, gases
or dust
2. Gloves which are chemical-resistant and impervious should always be worn when handing
the chemical products
3. Nomex coveralls (Flame resistant coveralls) should be worn in an event that there is a
chemical fire
4. A thermally insulating steel toe boot which covers the ankle should be worn to prevent
harm from falling objects or compression or risk of chemical fires
5. Industrial safety helmets to prevent harm of falling objects or bumping of head
6. Airmuffs or airplugs can be used to protect the users exposed to noise levels above 85dB
7. Respiratory protective equipment should be worn in the oxygen-deficient atmosphere
 NOISE POLLUTION (Rachel)

Sound is defined as a vibration that the human ear detects in terms of pitch and volume whereas
noise is defined as any unwanted sound. Noise pollution refers to unwanted or displeasing sound
produced which causes a disruption in human life. The unit of measurement for sound intensity or
the sound pressure level is the decibel (dB). However, A-weighted decibels (dBA) refer to an
expression of how the relative loudness of sounds in air is perceived by the human ear.

Equivalent continuous sound pressure level (Leq) is the average sound level over a given period
of time, usually thirty minutes and is expressed in terms of dBA. On the other hand, instantaneous
unweighted peak sound pressure level (Lpeak) refers to that value of the “unweighted” peak sound
intensity of a sound as measured at a specific location which is expressed in decibels (dB).

Hearing loss is depends on:

1. The intensity of the noise

2. The duration of the noise
3. Frequent exposure to the noise

Healthy tiny hair like cells located in the cochlea of the ear are understood as being the key to good
hearing. Even though as the aging process progresses, some die off naturally, many more are killed
early if unprotected exposure to hazardous noise occurs. When people are overexposed to noise,
symptoms such as temporary threshold shift, where a muffled sound occurs after noise exposure
and tinnitus, where a constant ringing in the ears is experienced. For both symptoms, if continued
overexposure occurs, it may worsen and even become permanent.

In terms of the legal requirements, the Noise Pollution Control Rules, 2001 (NPCR) refers to
legislation which was developed under the Environmental Management Act Chapter 35:05. These
Rules set prescribed standards for noise and for closely monitoring and controlling the emissions
of sounds to the environment.

The Prescribed Standards are shown in the figure below as outlined by the Environmental
Management Authority (EMA):
Once an activity is expected to exceed the limits outlined by the Environmental Management
Authority (EMA), a noise variance has to be applied for to the EMA. The NPCR refers to a
‘Variation’ as any sound level which deviates from the prescribed standards or acceptable sound
levels. However, once approval is granted by the EMA, the document enables the applicant to vary
from the prescribed standards but the level of sound which can be emitted is also limited.
Environmental noise monitoring may be a requirement for an industrial facility based on the
facility’s Certificate of Environmental Clearance (CEC) issued by the Environmental Management
Authority (EMA).

In order to control noise hazards in the industry, the source of the noise can be reduced through
repairs or upgrading of equipment displaying abnormal vibrations or noises. Also, the path of the
noise can be interrupted by using acoustic insulation or by enclosing the equipment in a separate
room.

When the sound level, measured using a sound level meter, exceeds 85dB, employee protection is
required. This protection is achieved by using Personal Protective Equipment such as the ear plug
or the ear muff which helps to reduce the sound waves traveling to the ear drum.
HSE ON THE DE-PROPANIZER AND DE-ETHANIZER COLUMNS (Rachel)

As aforementioned, the components used are highly flammable and some are simple asphyxiants.
Therefore, it is advised that plant personnel wear the proper PPE such as flame resistant coveralls,
steel toe boots, safety helmet, safety glasses, air muffs and respirator etc. Insulation was placed on
the overhead or distillate pipelines since the temperatures would be extremely cold as well as the
bottoms pipelines where the temperatures are extremely hot. Warning labels were placed on the
pipelines as a precautionary measure to indicate the hot or cold surface.

The main priority of a chemical plant is to ensure that safe operation is in effect. This is extremely
pertinent since a potential disaster could lead to major negative repercussions. Therefore, control
and instrumentation is seen as very essential for any chemical plant. In the columns, there were
measuring and indicating instruments such as flow meters and pressure indicators which were
strategically placed in order to measure and ensure that the process variables, such as flow and
pressure respectively, were operating within the safe limits.

Also, alarms were installed in order to alert the operators whether there was a deviation from the
set point of the process variables. For example, if the pressure indicator measures a high pressure
in the main line, the pressure controller would open the relief valve. However, if the relief valve
fails shut, the controller would shut off the pump in the main line and open the bypass line in order
to ensure the continued operation.

REFERENCES

(2019). Retrieved from https://www.ema.co.tt/images/Files/pdf/noisefaq_booklet.pdf

(2019). Retrieved from https://www.airgas.com/msds/001022.pdf

(2019). Retrieved from http://www.megs.ca/MSDS/Pdf/1-Pentene.PDF

(2019). Retrieved from https://www.airgas.com/msds/001009.pdf

Health, safety and environmental (Andrea)

In this section we look at the health and safety aspects of the de-methanizer distillation column and its reboiler and condenser. We also
look at the material safety data sheet for the components of Ethane, Propylene and Propane.

Risk Assessment: De-methanizer distillation column

Risk assessment

Equipment De-methanzier distillation Column operation

Risk ranking Low = low priority to be Moderate= medium priority to be High = high priority to be acted
implement when resources allow scheduled as soon as practicable upon immediately

Task/ Element Hazardous Likelihood Consequence Hazard control Revised Actions by

Situation of event ranking
What if

If V-301 in feed Damage to pump, moderate Process upset, now liquid Open valve V-305 on low Operator
line fails P-301 going into column the bypass line
If pump, P301 Pump fails or moderate Drives to low level. Damage Open P-302 in bypass Low Operator
fails to pump shutdown to equipment line

If valve V-309 No flow into High Rupture of pipeline with Emergency shutdown Moderate Operators an
fails distillation pump pressure. of equipment. technician
column

If build-up of Damage to Moderate Pressure build can cause the Open V-331 to relief Low Operator
pressure in column equipment to blow the pressure
distillation
column

There is a Catastrophic Very low Damage of equipment Design column with Very low Operators
failure in the failure of vessel indicators, alarms and
distillation controls for pressure
column and temperature.

Leak in pressure Release of Very low Flammable atmosphere Design a vent system if Very low operators
relief valve hazardous vapour vessel is in enclosed
Flammable liquids in
and liquid to area
environment
environment
Flammable vapors in
enclosure
Leak Rupture of Low Flammables substances in Design vessel with low operators
downstream of connection, open environment. Valves at both top and
distillation valve allows bottom stream, in order
Environmental pollution
column hazardous to close to prevent it
substance to from further spillage
atmosphere

Reflux level to Failure to start moderate Overfill of reflux tank Set high level alarm Low Technicians
high reflux pump LA-1 to indicate level
in reflux vessel.

Reflux level is Starts reflux Moderate Process upset Set love level alarm, Low Technicians
too low pump when level LA-1 to indicate level
is low in reflux vessel

Fail to set reflux Set reflux back Moderate More of less products to Place pressure Low Operators
back pressure pressure too low distillate is expected indicators when
correctly designing to alert
operator

Air gets into Pump would not moderate Pump cavitation Ensure operators are Low Operators
pump start train for state-up of
equipment.
Pump would not start
 Instill values before
and after pump for
priming

Valve V321 Damage to low Pump dry out Place vales before and Very low operators
fails open equipment after V-321 so it can be
turned off.
Flooding of distillation
vessel

Build-up of Rupture of Moderate Fragments of equipment Emergency shutdown low employees

pressure in the Condenser would be airborne. of equipment.
condenser

Danger to onsite personnel

Loss of production hours

Failure to open Loss of cooling to low Can fill tops stream with Locate flow indicators Low
V-1 to start a C-301 liquid and plug streams. and a lock off valve
cooling flow
 Rupture of pipelines and
damage to equipment and
personnel on site

The reboiler Equipment Moderate Burn out of equipment Install level alarm to low Operators
level is low damage heating medium indicate low levels on
reboiler to.

Stop pump P-305 so

Pump dry out
level would build up

V-4 value fail Buildup of Low Rupture of distillation Monitor temperature in Very Operators
open temperature and column distillation columns by Low
pressure in install temperature
column control, indicators and
Fragments of equipment alarm.
would be airborne

Damage of nearby
equipment

Loss of production ours

V-4 valve fail No stream Low Buildup of liquid Install flow meters to Very low Operators
close entering reboiler stream line and
monitor process
Flooding in distillation
column bottoms

V-4 valve fails Buildup of Low Rupture of heating lines in Instill flow meters on Very low Operators
Close condensate in reboiler condensate line
reboiler

Damage of equipment and Monitor process

nearby personnel closely

Condensate goes into stream

in line and may plug line

V-323 fails Buildup of liquid Low Rupture of process lines, Open V-327 in bypass Very low Operators
close/ isn’t open loss of production line so process would
continue without a
disruption
Install flow meters to
process lines
With respect to the distillation Column equipment safety, all personnel on site on the plant are to
wear they personal protection equipment, which include hard hats, safety glass, steel tip boots
and coveralls. Hot and cold lines of the process are to be insulated and label. Condensate and
reboiler lines are to be insulated due to the cold temperatures they would be working at. And the
equipment should be label.

Health, safety and environment of process chemicals (Andrea)

Component: Ethane

Section 1: Hazard Identification

Classification of substance or mixture: Flammable gas- category 1

Gas under pressure- compressed gas

Hazard Pictogram:

Signal words: Danger

Hazard statement: Extremely flammable gas, may form explosive mixture with air. Contains gas
under pressure. May displace oxygen and cause rapid suffocation

Section 2: First aid measures

Description of necessary first aid measures

Eye contact: Immediately flush eyes with plenty of water, occasionally lifting upper and lower
eyelid. Check and remove contact lenses. Continue to rinse for at least 10 minutes. Get medical
attention if irritation occur

Inhalation: Remove victim to area of fresh air and keep at rest in comfortable position
for breathing. If not breathing, or breathing becomes irregular, also if respiration arrest occurs,
provide artificial respiration or oxygen by trained personnel. It may be dangerous to provide
mouth to mouth resuscitation. Get medical attention if adverse health effects are severe. If
unconscious, place in recovery position and get medical attention immediately

Skin Contact: wash contaminated skin with soap and water. Remove contaminated clothing and
shoes. To avoid the risk of static discharge and gas ignition, soak contaminated clothing
thoroughly with water before removing it. Get medical attention if symptoms occur. Wash
clothing and clean shoes before reuse.

Ingestion: As this product is gas, refer to inhalation section.

Most important symptoms/ effect, acute and delayed

Potential acute health effects

Eye contact: Contact with rapidly expanding gas may cause burns or frostbite.

Inhalation: No known significant effects or critical hazards.

Skin Contact: Contact with rapidly expanding gas may cause burns or frostbite.

Frostbite: Try to warm up the frozen tissues and seek medical attention.

Ingestion: As this product is gas, refer to the inhalation section.

1
There is no specific data for over exposure to ethane for over-exposure sign/symptoms.

Section3: Handing and storage

Precautions for safe handling

Protective measures: Put on appropriate protective equipment avoid breathing gas. Use only with
adequate ventilation. Wear appropriate respirators when ventilation is inadequate. Don’t store in
confined areas. Close valve after each use and when empty protect vessel from physical damage.
Use only non-ignition tools. Avoid contact with eyes, skin and clothing.

Advice on general occupational hygiene: Eating, drinking and smoking should be prohibited in
areas where this material is handled, stored and processed. Workers should wash hands and face
before eating, drinking and smoking. Remove contaminated clothing and protective equipment
before entering eating areas.

Conditions for safe storage: Store in accordance with local regulations. Store in segregated and
approved areas. Store away from direct sunlight in a dry, cool and well-ventilated area, away
from incompatible materials. Eliminate all ignition sources.

Section 4: Exposure controls/ personal protection.

Hand protection: chemical- resistant, impervious gloves complying with an approved standard
should be worn at all times when handling chemical product.

2
Body Protection: Personal protective equipment for the body should be selected based on the
task being performed and the risks involved and should be approved by a specialist before
handling this product.

Other skin Protection: Appropriate footwear and any additional skin protection measures
should be selected based on the task being performed.

Respiratory protection: Select a respirator that meets the appropriate standard or

certification. Respirators must be used according to a respiratory protection program to ensure
proper fitting, training and other important aspect of use.

Component: Propylene

Section 1: Hazard identification

Classification of substance: Flammable gases- Category 1

Gases under pressure – Liquefied gas

Hazard pictogram:

Signal words: Danger

Hazard Statement: Extremely flammable gas. May form explosive mixture with air. Contains gas
under pressure; may explode if heated. May displace oxygen and cause rapid suffocation.

3
Precautionary statement

General: Read and follow material safety data sheet. Read label before use. If medical advice is
needed, have product container or label at hand. Close valve after each use and when empty. Use
equipment rated for cylinder pressure. Do not open valve until it is connected to equipment.

Prevention: Keep away from heat, hot surfaces, sparks and open flames or other ignition sources.
No smoking

Responds: Do not extinguish, unless leak can be stopped safety. Eliminate all ignition sources if
safe to do so.

Storage: Protect from sunlight. Store in a well-ventilated place.

Section2: First aid measures

Description of necessary first aid measures.

Eye Contact: Immediately flush eyes with plenty of water, occasionally lifting upper and lower
eyelid. Check and remove contact lenses. Continue to rinse for at least 10 minutes. Get medical
attention if irritation occurs.

Inhalation: Remove victim to area of fresh air and keep at rest in comfortable position for
breathing. If not breathing, or breathing becomes irregular, also if respiration arrest occurs,
provide artificial respiration or oxygen by trained personnel. It may be dangerous to provide
mouth to mouth resuscitation. Get medical attention if adverse health effects are severe. If
unconscious, place in recovery position and get medical attention immediately

Skin Contact: flush contaminated skin with plenty of water. Remove contaminated clothing and
shoes. To avoid the risk of static discharge and gas ignition, soak contaminated clothing
thoroughly with water before removing it. Get medical attention if symptoms occur.

Ingestion: as this product is a gas, refer to inhalation section.

Most important symptoms/ effect, acute and delayed

4
Potential acute health effects

Eye contact: No known significant effects or critical hazard.

Inhalation: No known significant effects or critical hazard.

Skin Contact: No known significant effects or critical hazard.

Frostbite: Try to warm up the frozen tissues and seek medical attention.

Ingestion: As this product is a gas, refer to the inhalation section.

There is no specific data for over exposure to ethane for over-exposure sign/symptoms.

Section3: Handing and storage

Precautions for state handling

Protective measures: Put on appropriate protective equipment to avoid breathing gas. Handle
only with adequate ventilation. Wear appropriate respirators when ventilation is inadequate.
Don’t store in confined areas. Close valve after each use and when empty, protect vessel form
physical damage. Use only non-ignition tools. Avoid contact with eyes, skin and clothing.

Advice on general occupational hygiene: Eating, drinking and smoking should be prohibited in
areas where this material is handled, stored and processed. Workers should wash hands and face
before eating, drinking and smoking. Remove contaminated clothing and protective equipment
before entering eating areas.

Conditions for safe storage: store in accordance with local regulations. Store in a segregated and
approved area. Store away from direct sunlight in a dry, cool and well-ventilated area, away from
incompatible material. Eliminate all ignition sources.

5
Section 4: Exposure controls/ personal protection.

Hand protection: chemical- resistant, impervious gloves complying with an approved standard
should be worn at all times when handling chemical product.

Body Protection: Personal protective equipment for the body should be selected based on the
task being performed and the risks involved and should be approved by a specialist before
handling this product.

Other skin Protection: Appropriate footwear and any additional skin protection measures
should be selected based on the task being performed.

Respiratory protection: Select a respirator that meets the appropriate standard or

certification. Respirators must be used accordance to a respiratory protection program to ensure
proper fitting, training and other important aspect of use.

Component: Propane

Section 1: Hazard identification

Classification of substance: Flammable gases- Category 1

Gas under pressure – Liquefied gas

Hazard pictogram:

6
Signal words: Danger

Hazard Statement: Extremely flammable gas. May form explosive mixture with air. Contains gas
under pressure; may explode if heated. May displace oxygen and cause rapid suffocation. May
cause frostbite.

Precautionary statement

General: Read and follow material safety data sheet. Read label before use. Keep out of
children’s reach. If medical advice is needed, have product container or label at hand. Close
valve after each use and when empty. Use equipment rated for cylinder pressure. Do not open
valve until it is connected to equipment.

Prevention: Keep away from heat, hot surface, sparks and open flames or other ignition sources.
No smoking.

Responds: Do not extinguish, unless leak can be stopped safety. Eliminate all ignition sources if
safe to do so.

Storage: Protect from sunlight. Store in a well-ventilated place.

Section2: First aid measures

Description of necessary first aid measures.

Eye Contact: Immediately flush eyes with plenty of water, occasionally lifting upper and lower
eyelid. Check and remove contact lenses. Continue to rinse for at least 10 minutes. Get medical
attention if irritation occurs

Inhalation: Remove victim to area of fresh air and keep at rest in comfortable position for
breathing. If not breathing, or breathing becomes irregular, also if respiration arrest occurs,
provide artificial respiration or oxygen by trained personnel. It may be dangerous to provide
mouth to mouth resuscitation. Get medical attention if adverse health effects are severe. If
unconscious, place in recovery position and get medical attention immediately.

7
Skin Contact: flush contaminated skin with plenty of water. Remove contaminated clothing and
shoes. To avoid the risk of static discharge and gas ignition, soak contaminated clothing
thoroughly with water before removing it. Get medical attention if symptoms occur.

Ingestion: Remove victim to fresh air and keep at rest in comfortable position for breathing. Get
medical attention if adverse health effects persist or severe. Ingestion of liquid can cause burns
similar to frostbite. If frostbite occurs get medical attention. Maintain an open airway. Loosen
tight clothing such as a collars, ties, belts or waistbands.

Most important symptoms/ effect, acute and delayed

Potential acute health effects

Eye contact: Liquid can cause burns similar to frostbite.

Inhalation: No know significant effects or critical hazard.

Skin Contact: Dermal contact with rapid evaporating liquid could result in freezing of the tissues
or frostbite.

Frostbite: Try to warm up the frozen tissues and seek medical attention.

Ingestion: Ingestion of liquid can cause burns similar to frostbite.

Over exposure to any categories above would adverse symptoms that include frostbite.

Section3: Handing and storage

Precautions for safe handling

Protective measures: Put on appropriate protective equipment to avoid breathing gas. Handle
only with adequate ventilation. Wear appropriate respirators when ventilation is inadequate.
Don’t store in confined areas. Close valve after each use and when empty, protect vessel from
physical damage. Use only non-spark tools. Avoid contact with eyes, skin and clothing.

8
Advice on general occupational hygiene: Eating, drinking and smoking should be prohibited in
areas where this material is handled, stored and processed. Workers should wash hands and face
before eating, drinking and smoking. Remove contaminated clothing and protective equipment
before entering eating areas.

Conditions for safe storage: store in accordance with local regulations. Store in a segregated and
approved area. Store away from direct sunlight in a dry, cool and well-ventilated area, away from
incompatible material. Eliminate all ignition sources.

Section4: Exposure controls/ Personnel Protection

Appropriate engineering controls: use only with adequate ventilation. Use process enclosures,
local exhaust ventilation or other engineering controls to keep workers’ exposure to airborne
contaminant below the recommended or statutory limit.

Environmental exposure: emission from ventilation or work process equipment should be

checked to ensure they comply with requirements of environmental protection legislation.

Hand protection: chemical- resistant, impervious gloves complying with an approved standards
should be worn at all times when handling chemical product.

Body Protection: Personal protective equipment for the body should be selected based on the
task being performed and the risks involved and should be approved by a specialist before
handling this product.

Other skin Protection: Appropriate footwear and any additional skin protection measures should
be selected based on the task being performed.

Respiratory protection: Select a respirator that meets the appropriate standards or certification.
Respirators must be used according to a respiratory protection program to ensure proper fitting,
training and other important aspects of use.
9
Thermal Hazards: If there is a risk of contact with the liquid, all protective equipment worn
should be suitable for use with extremely low temperatures materials.

Water pollution (Andrea)

As we know, water pollution is the contamination of the water body which include lakes, ponds,
rivers and seas. Hydrocarbons pollution in water can come from a number of sources, such as
petroleum, pesticides or other toxic organic matter. With the MTO process, the water is produced
alongside the orfins. The water is removed by a separator before it enters the absorber, but as we
know the water would not be 100% pure to release into the environment or recycled back into
the plant without treatment first. Here we look at the various effects the effluent water with the
hydrocarbons would have on the environment if it is release back without treatment.

With the release of hydrocarbons either accidentally or deliberately, severe problems can arise.
The following are some of the effects that may occur:

1. Damage to organ system in human body

2. Carcinogenic and other toxins are released unto atmosphere

3. Environmental fires

4. Damage to ozone layer

5. Damage to marine ecosystems

These environmental effects can be reduced by phytoremediation, bioremediations and chemical

remediation

Phytoremediation is where the use of plants to remove contaminant from a contaminated site.
However, these mechanisms could not work for all hydrocarbons water pollution but those that
can, would use the rhizofilterion, which involving the roots of plants to absorbing the
contaminants and the phyto-degradation through the plant's metabolism are less cost effective
and also environmentally friendly.

10
Bioremediation is the used of microorganisms. Regarding two methods, bio augmentation and
bio stimulation. Depending on the concentration, bio stimulation can have a greater effect on the
growth rate of degrading microorganisms which allows for a cheaper clean up method.

Chemical remediation is the use of chemicals such solidifiers and dispersants.

Land Pollution (Czarina)

Possible causes of land pollution due to this project include:
 Improper disposal of waste water and chemicals
 Leakage of Process fluids into surrounding environment
Possible Pollutants considered in analyzing environmental effects with regards to land pollution
included all liquid components such as MEA, Pentene and Waste Water. Exposure to MEA is
toxic to animals and humans and poses serious health effects. Pentene also poses a threat to the
health of animals and humans.
Effects of Pollution include:
 Soil Contamination- Render Land unusable
 Contamination of Underground Water Supply – Leads to accidental ingestion
 Risk to health of animals and humans in polluted environs.
Measures to control/reduce the risk of entrance of these pollutants to the surrounding
environment include:
 Proper Disposal of Chemicals and waste products following guidelines outlines by Local
Environmental Laws.
 Regular Inspection and maintenance of plant to ensure there are no leaks or spills.
 Clean-up plan in the instance of a large spill or leak into environment.

11
 Site plan

Site Plan (Andrea)

For our site plan, there were four main factors we took into consideration when choosing an area.
They are

1. Access to road ways

2. Access to raw material needed
3. Located close to a port
4. Away from a residential area.

Each point was an important factor to take into consideration. With assess to roadways, we are
able to transport equipment when building the plant and when we are in full operation of the
plant, we can transport raw materials and products in and out of the plant would out any
problems. Taking consideration to asses to raw materials, this would lower the cost of
transportation to the plant site. Also choosing a location close to the port allows us to import and
export our products easier. The plant would also be located away from residential area due to if
there are any spillage of chemical or any emission would be harmful to residents living in the
area

In the figure below we look at a map of Trinidad to determine the location, we were to narrow
out search to the Point-Lisas. In this area we have access to the raw material, access to road way
and it is close to the Point-Lisas port. Point Lisas being an industrial area was best suited for the
propylene-ethylene plant.

Upon looking at the critera’s stated above, we strategically chose the St. Andrews area to build
methanol to olefins plant. In additions, by selecting and appropriate location, it would adversely
impact the operating and capital cost of plant. The picture below show a satellite view the area in
the St. Andrews area where the plant would be constructed.

12
Figure 25- Site Plan

(Source: Google world)

13
 Figure___: Site plan of propylene-ethylene plant.

Upon entering, you would be greeted by the plant’s security. They would ensure that all
personnel entering the plant would be recorded in case of an incident were to take place we
would have the number of persons on the plant. Then there is the car park located next to the
main office. A café would be built on the plant for shift workers to get food or snacks without
leaving the plant.

From the Raw materials is to the reactor. The other equipment such as the absorption unit, and
distillation columns are laid out as shown in the diagram. The road way would have access to the
distillation columns product. Here it would be easier to transport the products out of the plant.

14
A control room is placed away from the equipment, as they would overseeing the process itself.
Another addition, a first aid station would be added, in case of any health issues or minor
injuries. A fire station would be added due major of the component are flammable substance.
Muster points 1 and 2 are added in case of any hazard that would take place, personnel on the
plant are able to make it to a safe area until official arrive on site for the situation.

15
 References

Salkuyeh. K and Adams II. A. (2015). Co-Production of Olefins, Fuels, and Electricity from

Conventional Pipeline Gas and Shale Gas with Near-Zero CO2 Emissions. Part I: Process

Development and Technical Performance

Pu Jianglong & Weng Huixin. (2013). Kinetic Modeling of Methanol to Olefins (MTO) Process

on SAPO-34 Catalyst. Journal of East China University of Science and Technology, Shangha.

Dr. M. Watson, UOPS410B, Fluidization, lecture notes.

Sinnott, R. K., Coulson, J. M., & Richardson, J. F. (2005). Coulson & Richardson's chemical
engineering. Oxford: Elsevier Butterworth-Heinemann.

Perry, R. H. and D. Green, eds., Perry’s Chemical Engineering Handbook (7th ed.),
McGrawHill, New York, 1997.

Fogler, H. S. (1999). Elements of chemical reaction engineering. Upper Saddle River, NJ:
Prentice Hall PTR.

Howard et al., 1992. Handbook of Environmental Degradation Rates. Chelsea, MI: Lewis
Publishers.

World Health Organization, Geneva (1997), Methanol Health and Safety Guide.

16