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MEMORANDUM

Date: March 12, 2016

To: Project Design Teams, The University of Utah

From: Jackson Ryan, Engineer, Clear Lake Plant


Celanese Chemical Group

Subject: Expansion of Celanese’s Singapore Acetic Acid Unit: Methanol Feedstock


Requirements

Celanese is considering an expansion of its Acetic Acid production facility at the


Singapore Plant. A project team is currently formed and working on the expansion of the
Acetic Acid production unit and is expected to increase production rates in 2020. To
support the new production rate a larger feedstock of methanol will be required.

The existing Acetic Acid Unit produces 500,000 metric tons/yr of acetic acid via
methanol carbonylation. The expansion project will increase the plant production rate to
1,250,000 metric ton/yr. The feedstocks for the carbonylation process are carbon
monoxide (CO) and methanol (CH30H). Several options have been suggested to obtain
the increased methanol requirement: (1) the entire methanol feed could be purchased
from the current methanol supplier, (2) Celanese could build its own methanol unit to
produce the additional required methanol, or (3) Celanese could build its own methanol
unit to produce the entire methanol feed required (and discontinue the purchase of
methanol from the outside supplier).

You are requested to investigate these three alternatives and recommend the most
economical choice. The project is scheduled to startup in January 2020. In performing
the economic analysis for this project, the project team should assume that one-third of
the capital investment will be made in the last half of the year 2018 and the other two-
thirds will be made during 2019. Also, your team may assume that the new methanol
production facility will operate at 75 percent of rated capacity during the first half of
2020 and at 100 percent of rated capacity during the second half of 2020. During all
subsequent years the plant is expected to operate at rated capacity. For the purpose of
this economic analysis, your project team should use a project operating life of twenty
years. In your economic analysis, the company would like for you to use a 10 percent
discount rate to determine, as a minimum, the net present value (NPV) for each option.

The project is on an extremely tight schedule to make the expansion startup in January
2020. A business/project team meeting will be scheduled during the week of April 23rd,
2016, where you will be asked to present your proposal.
PROJECT BACKGROUND

The Celanese Singapore Plant includes an acetic acid unit, which currently produces
500,000 metric tons/yr of acetic acid via methanol carbonylation. The carbonylation
process combines methanol and carbon monoxide to produce acetic acid:

CH3OH + CO  CH3COOH

The carbonylation process operates with a very high conversion (99.5%) of methanol to
acetic acid. The proposed expansion will increase the acetic acid production to 1,250,000
metric tons/yr. Currently, the CO is produced on site and the methanol is purchased from
an outside supplier. For the expansion project to be successful, the most economical
choice for the increased methanol requirement must be made. Three alternatives have
been proposed:

1. Simply purchase the entire methanol feedstock requirement from the current
supplier.
2. Build a methanol unit capable of producing the incremental demand for methanol
and continue the existing contract with the outside supplier for the currently
supplied amount of methanol
3. Build a larger methanol unit capable of producing the entire methanol requirement
and end the contract with the outside supplier.

The methanol unit that needs to be considered will be similar to the one operating at the
Celanese Bishop, Texas facility. The process converts synthesis gas (a mixture composed
mainly of CO, CO2, and H2), which is produced from natural gas. An existing synthesis
gas plant is on site in Singapore and has already been determined to be capable of
supplying the required synthesis gas feed. Methanol is produced from the syn-gas
through the following reaction:

CO + 2H2  CH3OH

As a first step towards further defining your problem and getting some preliminary
information, I suggest that you consult one of the company "techies". Joshua Jordan has
considerable experience in nearly all of the major production units in the company. Go
see him.
Later that day, with Joshua Jordan . . . . .

What did you say your name was? Oh. Nice to meet you. Yes, I am Joshua Jordan. You
can call me Floyd. I am a Senior Associate Global Staff Principal Process Engineer. I am
currently assigned to the Singapore Acetic Acid Expansion project team. Yeah, I have
been around for a while. What? You are asking me about the options we have for the
methanol feed for the Singapore acid unit? Why are you worried about that? Oh, your
boss said you should be worried about it. I can relate to that. Sure, I can give you a few
tips.

Let me look in my files to jog my memory. Hmmmm. Oh yes. Let's see. Methanol
production units. . . okay, here it is.

Here's the deal. We are planning to double the production of acetic acid from our
Singapore acetic acid unit. The unit produces acetic acid via methanol carbonylation. So
we are going to need twice as much methanol and CO as we are currently using. Luckily,
we have a CO unit available which is capable of producing all of the CO that we will
need. We also have a syn-gas unit that we think could produce all of the syn-gas that we
would need if we chose to produce our own methanol instead of buying it from an outside
supplier. You drew the short stick for the assignment to evaluate the cost of building our
own methanol unit and comparing that to what it’s costing us to buy methanol from
someone else. This is a tough exercise, but one critical to the success of this project.

OK, here’s some background about the methanol unit we want you to look at. The unit
runs on syn-gas, which is produced from natural gas. The syn-gas contains mainly CO,
H2, and CO2 but also contains some unconverted methane and a little bit of N2. The main
reactions that produce methanol are:

CO + 2H2  CH3OH (1)

CO2 + 3H2  CH3OH + H2O (2)

If you go look at some literature articles in the library, you’ll see that there is some
disagreement about whether or not reaction (2) actually occurs as I’ve written it. Most
people think that the CO2 is actually converted to CO first through the water-gas-shift
reaction:

CO2 + H2  CO + H2O (3)

This is an equilibrium reaction, which is actually favored in the reverse direction for the
way I’ve written the reaction. But as the CO is converted to methanol (and thus
consumed), some of the CO2 is converted to CO. The net result is that part of the CO2 in
the syn-gas feed is combined with H2 to make methanol and water. You will need to
program some kinetics for these reactions into your process simulation in order to create
a meaningful design. Later on, go talk to Tim Duncan about the kinetics. He has some
reaction kinetics that I used in a simulation once and they worked rather well. I’ll give
you more tips on the process simulation later, but first let me describe the process in more
detail.

The syn-gas is produced in a partial oxidation unit in which natural gas (mainly methane)
is essentially burned in a fuel rich environment to produce CO. Some of the methane
combusts completely and produces some CO2. The syn-gas feed that is available for our
use has the following typical composition:

Table I
Synthesis Gas Composition

Component Mole %
H2 73.72
CO 15.34
CO2 7.21
H2O 0.21
CH4 3.35
N2 0.16

The syn-gas comes from the syn-gas unit at about 500 psia pressure and is compressed in
a compressor to the desired reactor pressure. The gas is then fed to a packed bed reactor.
The reactor is basically a vertical shell and tube heat exchanger with catalyst in the tubes.
The reactant gases flow downward through the tubes (contacting the catalyst) and exit the
bottom of the reactor. Water is fed on the shell side to produce 500psig steam by boiling
and removing the heat of reaction. The reactor operates very nearly isothermally at a
temperature of 250 C. The catalyst is made of copper and zinc oxide on alumina pellets.

The hot gases exiting the reactor pass through a process heat exchanger, which is used to
preheat the feed gases and is then further cooled in a water-cooled heat exchanger. This
condenses the water and product methanol. The reactor product is then sent to a
separation system where the methanol is separated from the process by-products and any
unreacted gases. The unreacted gas stream is recycled to the suction of the syn-gas feed
compressor. In order to prevent the buildup of N2 and CH4, a portion of the recycle gas is
vented from the process. (Actually this vent stream is returned to the syn-gas unit where
it is burned for fuel credit at 2/3 fuel value.)

In addition to the main reaction which produces methanol, a couple of side reactions
occur which produce small amounts of light impurities (dimethyl ether and methyl
formate) and a heavy impurity (butanol). Randy can tell you more about the impurity
make rate. These impurities plus the by-product water must removed from the product
methanol stream in the separation system

Well, that’s it. Overall, the process is not too complicated but you will need to do quite a
bit of process simulation and design work to complete the project. You will need to
construct a process flow diagram (PFD) for the unit you design. You can use simplified
symbols for the equipment or whatever as long as it is understandable. It will be
important for your design team to identify the key process control issues/parameters, i.e.
what are the key parameters that need to be controlled and how should they be controlled.
Your design report should probably contain a table that presents this information.

You will need to do a preliminary process safety analysis on each of the options. What
do you mean you've never done one? Neither did I till I did my first one. I have included
some information (Appendix A) on doing a "what if" analysis. Basically, you are trying
to identify if there are any hazardous operations or chemicals in your designs. Always do
your safety study as a team effort and document it thoroughly. In this preliminary design,
your team should at least spend a page in your report documenting major safety concerns
you have about this process.

You are going to have to do a verbal presentation to the business team. I hope you can
keep your cool when you are talking to these guys. Aim your presentation at your
audience. Your audience will include a technical guy, but mostly will be business and
operations folks. You will only have 20 minutes to give your presentation.

You also want to present your economic analysis. You will have estimated each of the
options and performed an economic analysis for comparison. Be sure to state your
recommendations clearly. Tell them whether we should build our own methanol unit to
supply the increased methanol feed requirement or build our own methanol unit to supply
all of the needed methanol or simply continue buying methanol from our outside supplier.
Be clear in your recommendation. If there is further work or analysis that needs doing,
spell out clearly what needs to be done.

I don't know what else to tell you about the verbal presentation. Practice. If you are
doing a team presentation, practice with the team. Have someone else watch you and
critique you. Then ask that person what they did or did not understand.

I could go on and on here. Handouts, copies of your slides are nice. But if you give out a
handout, the audience will start reading that and you will lose some of the focused
attention on you and your team. Maybe you don't want the audience to focus on you. It
might be nice to give out copies of your slides after you've made your pitch. Have some
backup slides available if you think there will be questions on the details of your
economics, safety study, material balance, technical questions or whatever.

Good luck. Go see Tim about the reaction kinetics and see Manu Ginobili in accounting
for the economic data that you’ll need.
The next day, with Tim Duncan . . . .

Hi, I’m Tim. Joshua told me you’d be coming by. I guess he told you all about the
methanol process that you’re supposed to design, huh? I have some kinetics that I
developed a few years ago that he used in a process simulation. Unfortunately, we lost
his simulation when his computer died. I had a friend who told me once that “the
problem with computers is that once you let the smoke out they never work again.” Well,
anyhow, here is the info that you’ll need.

I assumed that all of the methanol is produced from the reaction of CO and H2:

CO + 2H2  CH3OH

I found a kinetic expression for this reaction in one of my old college textbooks. Here it
is:

rk
P P P
H2 CO CH3OH K equil

k A k P P
B H2 CO
 kC P
CH3OH
 2

where the partial pressures are in kPa, the reaction rate is in kmol/m3/s, and

k = 0.012
kA = 25781.8
kB = 1.4445x10-3
kC = 292.786
Kequil = 1.1146x10-4

Now, here is the clever part. Some of the CO2 that is fed to the reactor ends up getting
converted to CO through the water gas shift reaction:

CO + H2O  CO2 + H2

The way I handled this was to model it as two separate reactions:

CO + H2O  CO2 + H2 (1)

CO2 + H2  CO + H2O (2)

Since I knew that the equilibrium constant for the water gas shift reaction is about 85 at
the temperature that we run our reactors, all I did was assign reaction rates like this:

r1  85 PCO PH2O
r2  PCO2 PH2

And in these reactions, partial pressures are in kPa and reaction rates are in kmol/m3/s.
The result of treating the water gas shift reaction this way is that this reaction is basically
at equilibrium at all points in the reactor. Since the main reaction is in a standard
Langmuir-Hinshelwood form, you should be able to program that into your simulator.

In addition to the main reactions the process makes some impurities (some dimethyl
ether, methyl formate, and butanol). The stoichiometry of these reactions is:

2CO + 4 H2  C2H6O + H2O (dimethyl ether)


2CO + 2H2  CH3OCOH (methyl formate)
4CO + 8H2  C4H9OH + 3 H2O(butanol)

Don’t worry about the kinetics for these side-reactions. All you need to know is that we
make about 0.00024 lb dimethyl ether per pound of methanol, 0.0012 lb methyl formate
per lb of methanol, and 0.00026 lb of butanol per lb of methanol. Although the by-
product make rate is low it is important because the final methanol product must contain
less than 1 ppm of these impurities. Also, the product methanol must contain less than
1000 ppm of water.

Well, that should be enough to get you started. Let me know if you run into any
problems.
Later with Manu in Accounting . . . .

Hello. How are you doing? My name is Manu. You are new around here, eh? Well,
welcome aboard. You say you are working on the Singapore expansion project? Oh, just
the methanol part?

Well, I assume you’ll need some help with prices. Here is some stuff you may find
useful.

Item Cost of Item


Methanol 55 ¢/gal
Syn-gas $1.25 /MSCF
Fuel gas $5.00 /million BTUs
Electricity $0.04 /kWh
Demineralized water $0.08 /1000 gal
Water treatment $3.50 /1000 gal
Steam (500 psig) $3.50 /1000 lb
Catalyst $100 /ft3 of catalyst

What else? Let me see. I guess cooling water is somewhat confusing. Looking at my
notes I see that the cooling water is available at 90 F and should be returned to the
cooling tower no hotter that 115 F. Use an average cooling water cost of $0.10/1000 gal.

There is some other information you made need in determining annual costs. We have a
330-day year (on-stream time). We are down 2-3 weeks out of each year for turnaround.

Good luck. I hope the project proves out. We need to make more money so that I can get
a bigger bonus.
APPENDIX B
Process Safety Review Techniques – What if Method

The "what if" process safety review methodology is a general approach to hazard
evaluation. It differs from the other methods (HAZOP, Failure Mode and Effect
Analysis, Fault Tree) in that it is not as rigid systematically. The "what if" method
assumes a failure has occurred without regard (or probability) as to what caused it. The
"what if" methodology is particularly appropriate for preliminary design work.

"What if" questions are formulated for the entire process or a portion of it. These
questions are answered by the study team to evaluate the effects of component failures,
procedural failures, utility failures, and natural disasters with the aim of finding their
consequences.

As with other safety analysis techniques, the key is to combine the experience,
knowledge and creativity of each member of the process safety review team to identify
potential hazards. It is very important to document your study, including those items you
deem not to be hazardous.

Some of the "what if" questions/topics that should be addressed include the following
items. Note that not all of these may apply to a particular process or node of a process.

Loss of utilities

Steam Nitrogen Cooling water Caustic


Process water Boiler feedwater Fuel gas Antifoam
Service air Instrument air Heat exchange medium

Loss of electrical power and/or emergency power

Pressure safety valve or rupture disk relieving

Sufficient capacity Proper setting

Loss of computer control

Loss of fire water

Reaction or decomposition

Internal explosion or fire

What if operator fails to perform duties (all or partially)

The above list is not all-inclusive but should provide a good starting point.