CH

CHE655
Plant Design Project #7
Summer 2013
DESIGN OF A FORMALIN PRODUCTION PROCESS
(Courtesy of the Department of Chemical Engineering at West Virginia University,
University USA)

Introduction
Formaldehyde is an organic compound with the formula CH2O. It is the simplest aldehyde, hence
its systematic name methanal. Formaldehyde is a colorless gas with a characteristic pungent
odor. It is an important precursor to many other chemical compounds, espe
especially for polymers. In
2005, annual world production of formaldehyde was estimated to be 23 million tons (50 billion
pounds). Commercial solutions of formaldehyde in water, commonly called formalin, were
formerly used as disinfectants and for preservation of biological specimens.
Our company plans to evaluate the economics for a process to manufacture formaldehyde from
methanol. Currently, we buy formaldehyde for manufacturing adhesives and wish to explore
whether or not we would be better off manufacturing
manufacturing it for our own use. The consulting company
Designs-Are-Us
Us has recommended a process that employs a molybdenum oxide catalyst.
Your assignment is to evaluate the feasibility of a process to produce 50,000 tonne/y of formalin.
Formalin is 37 wt% formaldehyde
formaldehyde in water. Formaldehyde and urea are used to make ureaurea
formaldehyde resins that subsequently are used as adhesives and binders for particle board and
plywood.
A suggested process flow diagram (PFD) is shown in Figure 1. You should use this as a starting
s
point. However, any change that you can justify that does not violate the laws of nature is
allowed. Your job is to analyze the simplified styrene production process, to suggest profitable
operating conditions, and to write a final report summarizing
summarizing your findings.

Chemical Reaction
Unit 800 produces formalin (37 wt% formaldehyde in water) from methanol using a silver
catalyst process. Figure 1 illustrates the current process.
Air is compressed and preheated, fresh and recycled methanol are pumped and preheated, and
these two streams are mixed to provide reactor feed. The feed mixture should be about 39 mole
% methanol in air, which is above the upper flammability limit for methanol. (For methanol,
UFL = 36 mole %; LFL = 6 mole %.) In the reactor, the following two reactions occur:
CH 3 OH + 12 O2 HCHO + H 2O

(1)

CH 3OH HCHO + H 2

(2)

The selectivity for the first reaction to the second reaction is 9/1. The reactor effluent enters a
partial condenser in which most of the methanol, formaldehyde, and water are condensed with
the oxygen, nitrogen, and hydrogen remaining in the gas phase. The vessel, V-801, allows the
vapor and liquid phases to disengage, with the vapor leaving the process (to be burned to dispose
of the hydrogen), and with the liquid being separated in T-801 to recycle the methanol.

Process Details
Feed Stream and Effluent Streams
Stream 1: air feed at 25C and atmospheric pressure
Stream 2: methanol feed at 25C and atmospheric pressure, assumed pure
Stream 14: formaldehyde-water mixture, less than 1 wt% methanol allowed

Stream 15: deionized water at any pressure below source pressure, at source
temperature, mixed with Stream 14 so Streams 16-18 at 37 wt%
formaldehyde Stream 15:
Stream 18: formalin i.e., 37 wt% formaldehyde in water This is the stream that
must be at a flowrate equivalent to 50,000 tonne/y.
Equipment
Air Compressor (C-301)
increases the pressure of the feed air to 300 kPa, the compressor may be assumed
to be adiabatic with an efficiency of 70%.
Methanol Feed Pump (P-801 A/B)
increases pressure of methanol fed to 300 kPa, efficiency 80%
Heat Exchangers (E-801 and E-802)
E-801 heats methanol feed to 150C
E-802 heats (or cools if so, change utility) air to 200C, pressure drop of 25 kPa
on the process side for each heat exchanger
Reactors (R-801)
outlet temperature is at 200C, conversion in the reactor is 100% of the limiting
reactant, selectivity for the reaction in Equation 1 relative to the reaction in
Equation 2 is 9/1, 25 kPa pressure drop in heat exchanger portion, reactor is
actually wire gauze with catalyst supported above a shell-and-tube heat exchanger,
which must be sized, cost is for heat exchanger plus 25%
Heat Exchanger (E-803)
cools and partially condenses reactor effluent, pressure drop 25 kPa
Flash Vessel (V-801)
allows the vapor and liquid produced in E-803 to be separated, there is pressure
drop at inlet that can be designed for any value

Distillation Column (T-801)

Of the methanol in Stream 12, a sufficient amount enters Stream 13 so that the 1
wt% methanol constraint on Stream 14 is not violated. 99.5% of the
formaldehyde and water in Stream 12 enters Stream 14.
Heat Exchangers (E-804 and E-805)
reboiler and condenser, respectively, for T-801
Heat Exchanger (E-806)
cools product to between 35C and 45C, pressure drop specified in assignment
section
Pump (P-802 A/B)
provides pressure to pump formalin to storage tank
Tank (Tk-801)
storage tank for formalin, stores three days of product not shown on PFD

More Equipment Information

Pump (P-801 A/B)
The pump increases the pressure of Stream 3 to the reactor pressure. The pump work
should be calculated using the mechanical energy balance method taught in class.
Assume there is no temperature change across the pump. The cost of electricity to run the
pump is a utlility cost. The pump efficiency is 80%.
Compressor (C-801)
The compressor increases the pressure of the feed air to the reactor pressure. The
compressor may be assumed to be adiabatic. In that case, the compressor work, Ws, may
be calculated as
Ws = 4.5 R(Tout Tin )

(3)

where Ws is in [kJ/kmol] and the inlet and outlet temperatures, Tin and Tout, respectively,
are in [K]. The outlet and inlet temperatures are related through:

Tout

P
= Tin out
Pin

0.286

The cost of electricity to run the compressor is a utility cost. The compressor efficiency is
70%.
5

(4)

Heat Exchangers (E-801 and E-802)

If needed, these heat exchangers heat the feed streams so that Stream 8 is at the desired
reaction temperature.
Reactor (R-801)
Heat must be removed from the reactor so that the outlet temperature is at 200C. The
conversion in the reactor is 100% of the limiting reactant, and the selectivity for the
reaction in Equation 1 relative to the reaction in Equation 2 is 9/1.
Heat Exchanger (E-803)
This is a partial condenser, with the primary objective of condensing methanol,
formaldehyde, and water. For a given temperature and pressure, you may assume that all
light gases enter Stream 11, and that the other components distribute themselves based on
a bubble-point calculation.
Vessel (V-801)
This vessel allows the vapor and liquid produced in E-803 to be separated. The vapor
exits in the top stream, and the liquid exits in the bottom stream. The Streams 11 and 12
are at the same temperature and pressure as Stream 10. Stream 11 is vapor and Stream 12
is liquid.
Distillation Column (T-801)
This column runs at 1 atm. Separation of methanol from formaldehyde and water occurs
in this column. Of the methanol in Stream 12, a sufficient amount enters Stream 13 so
that the 1 wt% constraint on Stream 14 is not violated. 99.5% of the formaldehyde and
water in Stream 12 enters Stream 14.
Heat Exchanger (E-804)
In this heat exchanger, the some of the contents of the stream leaving the bottom of T-801
entering E-804 are vaporized and returned to the column. The amount returned to the
column is equal to the amount in Stream 14. The temperature of these streams is the
boiling point of the formaldehyde/water stream at the column pressure. The heat required
may be estimated by the heat of vaporization of each component at the boiling point of
water at column pressure. There is a cost for the amount of steam needed to provide
energy to vaporize the stream; this is a utility cost. The steam temperature must always be
higher than the temperature of the stream being vaporized, preferably at least 10C higher.
Heat Exchanger (E-805)
In this heat exchanger, the contents of the top of T-801 are condensed from saturated
vapor to saturated liquid at the column pressure. For this calculation, you may assume
that the pure methanol is condensed at its boiling point at the column pressure. There is a
cost for the amount of cooling water needed; this is a utility cost. The cooling water

leaving E-805 must always be at a lower temperature than that of the stream being
condensed, preferably at least 10C lower. The ratio of Stream 13 to the stream recycled
back to T-801 is 1/5.

Economic Analysis
When evaluating alternative cases, you should carry out an economic evaluation and
profitability analysis based on a number of economic criteria such as payback period, internal
rate of return, and cash flow analysis. In addition, the following objective function should be
used. It is the equivalent annual operating cost (EAOC), and is defined as
EAOC = (product value feed cost other operating costs capital cost annuity)
A negative value of EAOC means there is a profit. It is desirable to minimize EAOC; i.e., a
large negative value of EAOC is very desirable, although you are not being asked to carry out
optimization.
Utility costs are those for steam, cooling water, boiler-feed water, natural gas, and electricity.
The capital cost annuity is an annual cost (like a car payment) associated with the one-time,
fixed capital cost of plant construction and installation.
The capital cost annuity is defined as follows:

capital cost annuity = FCI

i(1 + i) n
(1 + i ) n 1

(12)

where FCI is the installed cost of all equipment; i is the interest rate; and n is the plant life, in
[y]. For accounting purposes, take i = 0.15 and n = 10.
For detailed sizing, costing, and economic evaluation including profitability analysis, you
may use the Aspen Process Economic Analyzer (formerly Aspen Icarus Process Evaluator) in
Aspen Plus Version 8. However, it is also a good idea to independently verify the final
numbers based on other sources such as cost data given below.

Other Information
You should assume that a year equals 8,000 hours. This is about 330 days, which allows for
periodic shut-down and maintenance.

Final Comments
As with any open-ended problem; i.e., a problem with no single correct answer, the problem
statement above is deliberately vague. You may need to fill in some missing data by doing a
literature search, Internets search, or making assumptions. The possibility exists that as you
work on this problem, your questions will require revisions and/or clarifications of the
problem statement. You should be aware that these revisions/clarifications may be
forthcoming.

Moreover, in some areas (e.g. sizing/costing) you are given more data and information than
what is needed. You must exercise engineering judgment and decide what data to use. Also
you should also seek additional data from the literature or Internet to verify some of the data,
e.g. the prices of products and raw materials.

References
1. Huang, X., N.W. Cant, M.S. Wainright and L. Ma, Chemical Engg. Proc. 44(3) 393-402
(2005).
2. Kirk-Othmer Encyclopedia of Chemical Technology Vol. 12, John Wiley and Sons, New
York (2005) p. 107.
3. Himmelblau, D. M. and J. B. Riggs, Basic Principles and Calculations in Chemical
Engineering (7th ed.), Prentice Hall, Englewood Cliffs, NJ, 2004.

Appendix 1
The reaction engineering group headed by I.M. (Shirley) Wright has obtained the following
kinetic information for the methanol oxidation reaction:
CH3 OH + 21 O2 HCHO + H2 O

(A-1)

The rate expression is:

rm1 [mole / g catalyst / hr ] =

k1 pm
1 + k 2 pm

(A-2)

where p is a partial pressure in atm, and m refers to methanol. The rate expression in Eq. (A2) is only valid when oxygen is present in excess. The constants in Eq. (A-2) are defined as:
ln k1 = 12.50 8774
T
7439
ln k 2 = 17.29 +
T

(A-3)
(A-4)

where T is in Kelvin.
Based on these data, the statistical mechanics group headed by Marge Inovera estimates rate
data as follows for the side reaction:
CH 3OH HCHO + H 2

(A-5)

The rate expression is:

rm 2 [mole / g catalyst / hr ] =

k1' p m0.5
0.5
1 + k 2' p m

(A-6)

The constants in Eq. (A-6) are defined as:

ln k1' = 16.9 12500
T
'
15724
ln k 2 = 25.0
T

(A-7)
(A-8)

To convert rate data from a catalyst-mass basis to a volume-of-reactor basis, take the catalyst
bulk density to be 1500 kg catalyst/m3 of reactor volume (void fraction is 0.5). The catalyst
particles are spherical, with a 1 mm diameter.
Standard enthalpies of reaction (298 K, 1 atm) for the two reactions are given as:

H1o = - 156 kJ/mol methanol

(A-9)

H 2o = + 85 kJ/mol methanol

(A-10)

Appendix 2
Economic Data
Equipment Costs (Purchased)
Note: The numbers following the attribute are the minimum and maximum values for that
attribute. For a piece of equipment with a lower attribute value, use the minimum attribute
value to compute the cost. For a piece of equipment with a larger attribute value,
extrapolation is possible, but inaccurate. To err on the side of caution, use the price for
multiple, identical smaller pieces of equipment.
Pumps

Heat Exchangers

Compressors

Compressor Drive

Turbine

Fired Heater

log10 (purchased cost ) = 3.4 + 0.05 log10 W + 0.15[log10 W ]2

W = power (kW, 1, 300)
assume 80% efficiency
log10 (purchased cost ) = 4.6 0.8 log10 A + 0.3[log10 A]2
A = heat exchange area (m2, 20, 1000)
log10 (purchased cost ) = 2.3 + 1.4 log10 W 0.1[log10 W ]2
W = power (kW, 450, 3000)
assume 70% efficiency
log10 (purchased cost ) = 2.5 + 1.4 log10 W 0.18[log10 W ]2
W = power (kW, 75, 2600)
log10 (purchased cost ) = 2.5 + 1.45 log10 W 0.17[log10 W ]2
W = power (kW, 100, 4000)
assume 65% efficiency
log10 (purchased cost ) = 3.0 + 0.66 log10 Q + 0.02[log10 Q ]2
Q = duty (kW, 3000, 100,000)
assume 80% thermal efficiency
assume can be designed to use any organic compound as a fuel

Vertical Vessel

log10 (purchased cost ) = 3.5 + 0.45 log10 V + 0.11[log10 V ]2

V = volume of vessel (m3, 0.3, 520)

Horizontal Vessel

log10 (purchased cost ) = 3.5 + 0.38 log10 V + 0.09[log10 V ]2

V = volume of vessel (m3, 0.1, 628)

Packed Tower

Cost as vessel plus cost of packing. Assume that HETP = 0.6 m.

Packing

log10 (purchased cost ) = 3 + 0.97 log10 V + 0.0055[log10 V ]2

V = packing volume (m3, 0.03, 628)

10

Tray Tower

Cost as vessel plus cost of trays

Trays
log10 (purchased cost ) = 3.3 + 0.46 log10 A + 0.37[log10 A]2
A = tray area (m2, 0.07, 12.3)
Storage Tank
log10 (purchased cost ) = 5.0 0.5 log10 V + 0.16[log10 V ]2
V = volume (m3 ; 90; 30,000)
Reactor, Adiabatic

Cost as 2 x (Cost of vessel based on volume)

Reactor with Heat Exchange

Cost as 2 x (Cost of vessel based on volume + cost of heat

exchanger based on area)

It may be assumed that pipes and valves are included in the equipment cost factors. The
location of key valves should be specified on the PFD.

Equipment Cost Factors

Total Installed Cost = [Purchased Cost] [4 + material factor (MF) + pressure factor (PF)]
Pressure Factors:
Pressure < 10 atm,
(absolute) 10 - 20 atm,
20 - 40 atm,
40 - 50 atm,
50 - 100 atm,

PF = 0.0
PF = 0.6
PF = 3.0
PR = 5.0
PF = 10

Material Factors:
Carbon Steel
Stainless Steel

MF = 0.0
MF = 4.0

does not apply to turbines, compressors,

packing, trays, or catalyst, since their cost
equations include pressure effects

11

Utility Costs
Low Pressure Steam (618 kPa saturated)

$7.78/GJ

Medium Pressure Steam (1135 kPa saturated)

$8.22/GJ

High Pressure Steam (4237 kPa saturated)

$9.83/GJ

Natural Gas (446 kPa, 25C)

$6.00/GJ

Fuel Gas Credit

$5.00/GJ

Electricity

$0.06/kWh

Boiler Feed Water (at 549 kPa, 90C)

$2.45/1000 kg

Cooling Water
$0.354/GJ
available at 516 kPa and 30C
return pressure 308 kPa
return temperature is no more than 15C above the inlet temperature
Refrigerated Water
available at 516 kPa and 10C
return pressure 308 kPa
return temperature is no higher than 20C

$4.43/GJ

Deionized Water
available at 5 bar and 30C

$1.00/1000 kg

Waste Treatment of Off-Gas

incinerated - take fuel credit

Refrigeration

$7.89/GJ

Wastewater Treatment

$56/1000 m3

Any fuel gas purge may be assumed to be burned elsewhere in the plant at a credit of
$2.50/GJ. Steam produced can be returned to the steam supply system for the appropriate
credit.

Catalyst, Feed and Product Prices

Methanol
Formaldehyde
Catalyst

$0.64 / kg
$0.99 / kg
$2.25 / kg / year

12

Appendix 3
Other Design Data
Heat Exchangers
For heat exchangers, use the following approximations for heat-transfer coefficients to allow
you to determine the heat transfer area:

situation

h (W/m2C)

condensing steam

6000

condensing organic

1000

boiling water

7500

boiling organic

1000

flowing liquid

600

flowing gas

60

13