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Process Description and ASPEN Computer Modelling of Formaldehyde

Production from Methanol
Article · April 2018
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Giuliana Maria Alvarenga Cicchelli Maria Panayi

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University of Groningen
BSc Chemical Engineering

WBCH17001 - Process Design
Course coordinator: dr. ir. J.G.M. (Jos) Winkelman

Course supervisor: Prof. dr. ir. Arjan Kloekhorst
Process Description and ASPEN Computer Modelling of Formaldehyde

Production from Methanol
Giuliana Maria Alvarenga Cicchelli S2895455

Diana Bollen S2987902
Maria Panayi S2933772
Process Description and ASPEN Computer Modelling of Formaldehyde Production from Methanol
April 20th, 2018
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April 20th, 2018
Table of Contents
1. Introduction ...........................................................................................................................................................4
2. Literature Survey and Process Description ...........................................................................................................5
2.1 Incomplete Conversion and Distillative recovery of Methanol ...........................................................................6
2.2 Formox process ...................................................................................................................................................7
2.3 BASF process ......................................................................................................................................................8
3. The BASF process in detail ..................................................................................................................................9
3.1 Gasifier ................................................................................................................................................................ 9
3.2 Reactor ................................................................................................................................................................ 9
3.2.1 Chemical Reactions in Reactor ....................................................................................................................9
3.3 Absorber ............................................................................................................................................................ 11
3.3.1 Technical Description of the Absorption Column ..................................................................................... 11
3.3.2 Mass Transfer and Chemical Reactions in Absorber ................................................................................. 11
4. Chronological Model Building in ASPEN .......................................................................................................... 13
4.1 Gasifier Modelling ............................................................................................................................................ 14
4.2 Reactor Modelling ............................................................................................................................................. 15
4.3 Absorber Modelling .......................................................................................................................................... 16
4.4 Overall Process Modelling Conclusions: .......................................................................................................... 19
5. Results and Discussion ....................................................................................................................................... 20
5.1 Collaboration with other groups ........................................................................................................................ 20
5.2 Mass balance ..................................................................................................................................................... 20
5.3 Energy balance .................................................................................................................................................. 22
5.4 Mass fraction of formaldehyde in Absorber ..................................................................................................... 22
5.5 Amount of formaldehyde in streams ................................................................................................................. 23
5.6 Conversion of methanol .................................................................................................................................... 23
5.7 Handling waste streams ..................................................................................................................................... 23
5.8 Further improvement ......................................................................................................................................... 23
6. Conclusion .......................................................................................................................................................... 24
7. Bibliography ............................................................................................................................................................ 25
Appendix A ................................................................................................................................................................. 27
Appendix B .................................................................................................................................................................. 28
Appendix C .................................................................................................................................................................. 28
Appendix D ................................................................................................................................................................. 29
Appendix E .................................................................................................................................................................. 30
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1. Introduction
Formaldehyde production from methanol is one of the most relevant processes in the field of Chemical
Engineering. It serves of great interest due to the large chemical utility formaldehyde can provide, since it
is an important precursor to a variety of chemical compounds. In this report, a formaldehyde production
unit (BASF process) is simulated using the computer programme ASPEN.
According to supervisor Arjan Kloekhorst, the model must meet several requirements:
- The formaldehyde solution obtained from the simulation must contain maximal weight percent of
formaldehyde, however not more than 50-55wt% since this results in explosion.
- The input of methanol is 25 ktonne/year = 2854 kg/hr.
- The methanol conversion must be as high as possible, to make the process more green and
sustainable.
- The off-gas stream coming from the absorber in the model must contain a very low concentration
of formaldehyde.
In order to successfully model a formaldehyde production plant, in-depth literature research had to be done.
The results of this research are presented in Chapter 2. In Chapter 3, the selected production process (the
BASF-process) has been explained in detail. In Chapter 4, it is presented how the model is built in ASPEN
chronologically. In Chapter 5, the results and discussion are presented, and Chapter 6 gives a conclusion.
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2. Literature Survey and Process Description
As mentioned in the introduction, the production of formaldehyde is a very important industrial process
due to the fact that it is the precursor for the manufacturing of a variety of other chemicals 1 as well as its
utilisation in other industries i.e. the Health Industry, where it is used in the production of vaccines. The
world production rate of formaldehyde in the year 2012 was of 32.5 million metric tons2 equivalent to
32500 million kg. The only factor that holds formaldehyde production back is its high reactivity, making
long-distance transportation virtually impossible3.
Regarding the transportation of formaldehyde, it is important to consider the allowed weight
percentage of formaldehyde in solution. The standard concentration of formaldehyde for pricing and
production data is 37 wt.%. But currently, industrial plants usually consume solutions up to 55 wt %
formaldehyde.
While evaluating the process, it is important to have an idea of its overall requirements. The general
and typical operating parameters for an almost complete conversion of a formaldehyde plant 4 are presented
in the table 1.
Table 1: Typical Operating Parameters of Formaldehyde Plant
Methanol Flow Rate 4667 kg/h
Methanol Purity 99 %
Methanol Quantity 4620 kg/h
Molar Methanol Flow Rate 144,375 mol/h
Molar Air/Methanol Ratio 1.87
Water Flow Rate 2364 kg/h
Water Purity 94 %
Actual Water Flow 2222 kg/h
Another factor to consider is air quality: the air introduced into formaldehyde plant usually contains a
variety of impurities i.e. acidic gases (CO2), salts, particulate matter etc. Consequently, the air has to be
passed through some kind of filter5.
1
See bibliography [1]
2
3
4
5
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April 20th, 2018
With this general idea in mind of the role of formaldehyde in the chemical industry, we can now consider
the various manufacturing ways that are currently employed for producing it. The main industrial methods
of formaldehyde production are: 1. Incomplete conversion and distillative recovery of methanol (silver
catalyst process), 2. Formox process and 3. BASF process: complete conversion of methanol (silver catalyst
process). A small description of these processes are given below.
2.1 Incomplete Conversion and Distillative recovery of Methanol6
In this particular process, partial oxidation takes place. A gasified mixture of pure methanol and air
combined with steam is fed into a reactor with excess methanol. The vapour is then passed through a
shallow catalyst bed of silver crystals. The operating temperature range is of 590-650 °C; the product
obtained contains formaldehyde solution is 50 - 55 wt% with a yield range of 91-92 mol%.
The weight percentage of formaldehyde in solution can be shifted i.e. lowered by reducing the
energy intensive distillation of methanol. The off-gas released is either released to the atmosphere or
combusted to generate steam. See figure 2.1.
Figure 2.1: “Incomplete Conversion and Distillative recovery of Methanol for

Formaldehyde Production”. Where a = Evaporator; b = Blower; c= Rector; d = Boiler;
e = Distillation column; f = Absorption column; g = Steam generator; h = Cooler; i =
Superheater, j = Anion-exchange unit.
6
Ullmann’s Encyclopedia of Industrial Chemistry, Section F: “Formaldehyde” p. 7
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April 20th, 2018
2.2 Formox process
The formox process 8 is slightly different than the silver-catalyst methods because it employs a metal oxide
as a catalyst. It works by passing the methanol feed into an evaporator (heated by steam), this feed is then
mixed with air and off-gas produced in the absorption tower. This new gas feed is then passed through a
heat exchanger reactor, where the tubes are filled with catalyst. The operating temperature range is of 270
- 400 °C and atmospheric temperature. Conversion is almost complete but it’s temperature dependent;
above 470 °C side reactions increase considerably. See figure 2.2.
Figure 2.2: “The Formox Process for Formaldehyde Production”. Where

a = Evaporator; b = Blower; c= Rector; d = Boiler; e = Heat exchanger; f
= Formaldehyde absorption column; g = Circulation system for heat-
transfer oil; h = Cooler; i = Anion-exchange unit.
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2.3 BASF process

The BASF process is comparable to the process of incomplete conversion and distillative recovery of
methanol since they both employ the same catalyst (silver catalyst); one of the greatest difference between
these two is that the BASF process gives complete conversion of methanol to formaldehyde. It works by
introducing a combined feed of gasified air, methanol and water (60:40 ratio of methanol to water) into a
fixed bed reactor equipped with a layer of silver catalyst. The temperature in the process varies depending
on the section that we’re considering, the reactor operates at a range of 600 - 700 °C.7 while the absorber
functions at a range of 40 - 70 °C. The process will result in a formaldehyde solution of about 50 wt%. See
figure 3.
Figure 2.3: “The BASF Process for Formaldehyde Production”. Where a = Evaporator; b = Blower; c=
Reactor; d = Boiler; e = Heat exchanger; f = Absorption column; g = Steam generator; h = Cooler; i =
Superheater. Recycling schemes: - ・– ・– off -gas, ---- formaldehyde solution. .
By evaluating all these three different methods, it was concluded that the most attractive process to consider
and to model was the BASF process, since it is described as giving the highest methanol conversion which
is most attractive when considering the sustainability of the process. A process with minimum product
waste has priority. When compared to the Formox process, the scale of a BASF plant is much smaller, this
is obviously desirable when considering operational convenience - it is also much more cost effective to
have a smaller plant since building cost would be considerably lower.
7
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April 20th, 2018
3. The BASF process in detail
In order to be able to model this process in detail, it is important to understand each and every stage of this
process. The whole system can be subdivided into three stages: the gasifier, the reactor and the absorber.
This following section will dive into the details of each stage; containing relevant information that was
found in literature.
3.1 Gasifier
The first step of the process is the vaporization of the feed mixture. This mixture consists
of methanol, water and air. Air is provided as fresh air but if needed air can also be taken
using a recycle stream from the absorption column, recycling off-gas from the last stage
of the column to the evaporator. The aim of the gasifier is to provide a gaseous outlet
product of a 60/40 ratio of methanol to water.
The operating conditions of the evaporator are such that the requirements of
the outlet composition are met and most importantly that the temperature remains below
the explosive limit of methanol-water-air mixture. In the case that a recycle stream is
used to provide air to the evaporator the explosive limits of methanol-water- Figure 3.1: The Gasifier
formaldehyde mixture have to be also considered. in the BASF Process
For safety reasons a demister is used to ensure that there are no liquid
droplets of any compound in the stream to be fed in the reactor. After the gaseous mixture passes through
the demister but before it is fed to the reactor it passes through a heat exchanger where superheated steam
is used to raise the temperature of the gaseous mixture to around 120˚C.The liquid stream of the evaporator
can be used in a stripping cycle. It can be heated using a heat exchanger linked to the first step of the
absorption column and fed back to the gasifier.
3.2 Reactor
After the desired gas composition is obtained, the next main step in this process is to convert the gasified
methanol/air/water stream into formaldehyde. See figure 3.2. This is done by passing the hot reaction gases
through a fixed-silver catalyst bed reactor (25 - 33mm bed of silver catalyst)8. In this reactor partial
oxidation occurs where the methanol is converted to formaldehyde.
3.2.1 Chemical Reactions in Reactor

The main chemical reactions taking place in the reactor:9
[1] CH3OH ↔ CH2O + H2 ΔH = +12.5 kJ/mol
8
Ullmann’s Encyclopedia of Industrial Chemistry, Section F: “Formaldehyde” p. 8, ‘Complete Conversion of
Methanol (BASF) process’
9
Ullmann’s Encyclopedia of Industrial Chemistry, Section F: “Formaldehyde” p. 7
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April 20th, 2018
[2] H2 + ½ O2 → H2O ΔH = -243 kJ/mol
[3] CH3OH + ½ O2 → CH2O + H2O ΔH = -159 kJ/mol
There are also other (less relevant) reactions forming byproducts:
[4] CH2O → CO + H2 ΔH = +12.5 kJ/mol
[5] CH3OH + 3/2 O2 → CO2 + 2 H2O ΔH = -674 kJ/mol
[6] CH2O + O2 → CO2 + H2O ΔH = -519 kJ/mol
The reactor operating temperature is relatively high (600 - 720 °C)10 and the operating pressure is
atmospheric. The reactor itself is equipped with a boiler, where superheated steam cools the produced
formaldehyde gas to a lower temperature of 150°C - this is essential to avoid formaldehyde
decomposition.11 The output of the reactor is consequently a “Dry gas”12 this stream is then connected to
the absorber.
Figure 3.2: Showing the position of the reactor in the BASF process.
10
Ullmann’s Encyclopedia of Industrial Chemistry, Section F: “Formaldehyde” p. 6, ‘Silver Catalyst Processes’
11
Ullmann’s Encyclopedia of Industrial Chemistry, Section F: “Formaldehyde” p. 5 ‘Chemical Properties’
12
Dry gas: “Gases containing less than 0.1 gallon of condensables pero 1000 cubic feet of produced gas.” See
bibliography [7]
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3.3 Absorber
Because of the difficulty to handle formaldehyde in its pure gasified form, in industry it is usually utilized
in its aqueous form. This can be achieved by doing the following: After the gaseous stream containing the
produced formaldehyde is obtained, the full gas-phase stream is inserted in the feed of an absorber; where
the aim is to absorb the formaldehyde in water and obtain a 55 wt% solution of formaldehyde in water.
3.3.1 Technical Description of the Absorption Column

In this absorber, water flows from the top of the column downwards, in such
way that the gas-liquid contact is countercurrent; countercurrent contact is
usually preferred because it means less stages will be required to achieve the
same separation (column height lower) compared to a non-countercurrent
contact. This water not only helps with formaldehyde absorption, but also
helps by taking up heat from the column - this is useful for needed
temperature control; because of the exothermic equilibrium reaction of
formaldehyde and water (see equation [7] below) with a corresponding
enthalpy change of -31.4 kJ/mol causing an expected temperature increase.
[7] CH2O + H2O ↔ CH2(OH)2 ΔH = -31.4 kJ/mol13

Figure 3.3: Showing a
schematic drawing of
To have significant temperature regulation, it can be seen from figure 3.3 that absorber.
each of the absorption beds has an external liquid recirculation system that is
fitted with heat exchangers. The overall operating temperature range of the absorption column is 20 °C -
70 °C and it operates at atmospheric pressure.
3.3.2 Mass Transfer and Chemical Reactions in Absorber
When there is gas-liquid contact there is not only heat transfer - there is also mass transfer that needs to be
considered. A significant chemical interaction occurs because formaldehyde reacts with water to form
methylene glycol as discussed above and seen from equation [7].
The reaction of formaldehyde and water is to be expected, because formaldehyde itself is highly
reactive. The formation of methylene glycol also gives way to consequent multiple polymerization
reactions. Below is a general and simplified scheme of the unavoidable polymerizations.
Given that:
MG = Methylene glycol = HO-CH2-OH = WF

F(g) = Formaldehyde gas phase
F(l) = Formaldehyde liquid phase
W = Water
13
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F(g) → F(l)
F + W ↔ WF
WF + WF ↔ WF2 + W (HO-CH2-O-CH2-OH) (dimer)
WF + WFi-1 ↔ WFi + W (general oligomer )
The formation of these oligomers are in theory not so problematic, as it is technically a way of formaldehyde
storage. Due to the reversibility of the reaction, formaldehyde can be re-obtained by shifting the equilibrium
(removal of water) to the left side.
At the end, the output of the absorber is a formaldehyde in water solution of 55 wt%. There is also
an off-gas stream that comes out of the top of the column, for a very efficient extraction of formaldehyde,
the wt.% of formaldehyde and methylene glycol in this stream should be as low as possible: preferably
below 2 wt.%.
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4. Chronological Model Building in ASPEN
The block diagram of the process is given below.

Lucidchart
Figure 4.1: The block diagram of formaldehyde production from methanol
The PFD of the model simulated in Aspen is given in Appendix A. In this Chapter, the model building is
explained chronologically.
The blocks in the model are divided in three sections. The first section contains the mixer that mixes
methanol, water and air; the evaporator and the heat exchanger which heats up the gas stream using
superheated steam. The second section contains the reactor and the heat exchanger which cools down the
stream to 150°C. The third and last section contains the absorption column, the splitter and four heat
exchangers. The following unit codes are used for each block:
M – Mixer
C – Column
X – Heat Exchanger
R – Reactor
S – Splitter
The heat exchanger cooling down the stream leaving the first stage of the absorption column is called X301.
However, in Aspen the numbering of the stages is the other way around: the first stage in a real life
absorption column is the last stage in the column when modeling in Aspen. Therefore, in the model the gas
leaving the first stage (4th stage in Aspen) is cooled down by a heater with unit number 01.
The streams are named following XYY with X being the section number and YY being the two-digit stream
number. For example: stream 301 is the stream that goes into the absorber (which is in section 3) and stream
303 is the stream leaving the first stage of the absorber.
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4.1 Gasifier Modelling

An Aspen simulation of the BASF process was carried out using the flow diagram shown in Figure 2.3 as
a model. The first step was the determination of the evaporator [C101] feed stream [104]. This stream [104]
was created using a mixer [M101]. An air stream [101], methanol stream [102] and water stream [103] were
combined. As the methanol intake for our process was given by the supervisor to be 25 ktonne/yr (= 2854
kg/hr)14, we used the chemical reaction equation [8] to calculate the amount of oxygen which was found to
be 1426.95kg/hr (equals to approximately 6795 kg/hr of air).
[8] CH3OH + ½ O2 → CH2O + H2O
To determine the flow of water [103] to be used as a feed we used a trial and error method to make the
evaporator work. Starting from a water flow of 1500 kg/hr the evaporator was giving an error as nothing
was present in the outlet liquid stream [105]. With a water flow of 3000 kg/hr the evaporator was working
properly.
From the literature sources used for this simulation it was known that the gaseous outlet of the
evaporator [106] which would be heated and fed into the reactor should have a “methanol/water mass ratio
typically 60/4015. In order to achieve this ratio a design specs was carried out varying the temperature of
the evaporator column. This was giving 65°C as the optimum temperature for the determined process
parameters, however when using this temperature at the evaporator the desired mass ratio in stream [106]
was not obtained, a value of methanol/water of 1.537 instead of 1.5 was obtained. The solution to this
problem was to decrease the tolerance of the design specs to 0.000005 and run it again. This gave a new
temperature close to 66°C. Introducing this condition in the evaporating column, gave a mass fraction for
methanol of 0.232168 and a mass fraction for water equal to 0.154995 giving a methanol/water ratio of
1.4979, a value really close to the desired one.
The next requirement to be met in the simulation was to heat the gaseous stream [106] to a
temperature of 600°C. A heat exchanger unit [X101] using a superheated steam medium [107] (temperature
of 800°C and flow of 15000 kg/hr) was ideal for this application. This medium was cooled to 545°C [108],
increasing the temperature of gaseous outlet stream of the evaporator [106] from 66°C to 600°C in stream
[201] which was the feed to the reactor [R201].
14
See ‘Introduction’
15
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4.2 Reactor Modelling

Modelling the reactor required some assumptions to be made. In reality the presence of the catalyst would
mean that a plug flow reactor is the ideal one to be used. However, there were many variables required to
be known for simulating such a reactor something which we did not have. It was therefore decided to
simulate the reactor as an equilibrium one. The reactor to be used in the process would have predetermined
working conditions. It would be working at a specified temperature (650°C) and pressure (1.01325 bar),
both constant over time. This means that an equilibrium reaction could be used as a non-equilibrium one.
The equilibrium would only be affected (shift to one or other side) if there was a temperature or
pressure change. In this case, these factors were not changing so a Stoichiometric Reactor was used instead
of an Equilibrium one, working as the reaction is a non-equilibrium reaction.
Simulation of the Stoichiometric reactor required literature values16, specifically methanol
conversion and formaldehyde selectivity with the numbers being 97.15% and 89.24% respectively. This
meant that 89.24% of the 97.15% of methanol reacting is converted to formaldehyde, thus
(89.24%*97.15%) 87% of methanol is reacting to methanol. To get these specified numbers we used two
stoichiometric reactors. In the first reactor we introduced the reactions shown on figure 4.2, with
corresponding fractional conversions given in table 4.1. The reaction introduced in the second reactor
[R202] is given in figure 4.3, with corresponding fractional conversion given in table 4.2.
Figure 4.2: The reaction equations used for the simulation of the first Stoichiometric reactor [R201].
Reaction number Fractional conversion Of Component

1 0.95 Methanol
2 1 Hydrogen
3 0.0215 Methanol
Table 4.1: The fractional conversion of the reactions defined in the “Stoichiometric Reactor” [R201] as shown in
figure 4.2
16
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Figure 4.3: The reaction equation used for the simulation of the first Stoichiometric reactor [R202].
Reaction number Fractional conversion Component

1 0.08 Formaldehyde
Table 4.2: The fractional conversion of the reaction defined in the “Stoichiometric Reactor” [R202] as shown in figure
4.3
At first the two reactions forming formaldehyde (reactions [1] and [3] section 3.2) were combined giving
Reaction 1 in Figure 4.2. The reaction of methanol with oxygen (reaction [5] section 3.2) was also defined
as Reaction 3 in [R201] as it also consumes a small amount of methanol. The fractional conversion of the
two reactions was specified as 0.95 and 0.0215 of methanol respectively, giving the desired total conversion
of methanol (0.9715). The second reactor [R202] was used to introduce the reactions consuming
formaldehyde (by adding reactions [4] and [6] of section 3.2), with the fractional conversion set to 0.08
consumption of formaldehyde. This means that from the formaldehyde produced in [R201] using 0.95 of
methanol, a small amount (0.08) of formaldehyde is consumed to byproducts, thus giving the desired value
of 0.87 of methanol used towards formaldehyde production. The last reaction ([2] section 3.2) was
introduced as well in the simulation, Reaction 3 figure 4.2, with the fractional conversion of hydrogen set
to 1, assuming that all of the hydrogen is converted to water.
Using table 4.3 one can prove that the conversion of methanol to formaldehyde is 87% while the overall
percentage of methanol is 97.15% (see calculations in Appendix B
Mole flow in kmol/hr

Component Stream 201 Stream 203
FORMALDEHYDE 0 70.3421
WATER 96.62823 141.377
METHYLENE GLYCOL 0 0
HYDROGEN 0 41.2877
CARBON MONOXIDE 0 3.05835
OXYGEN 44.57012 19.8015
CARBON DIOXIDE 0 4.78873
METHANOL 80.48293 2.29376
NITROGEN 191.5819 191.5819
Table 4.3: Composition of inlet [201] and outlet [203] streams of the stoichiometric reactors.
The outlet stream of the reactor was then cooled down to 150ºC using a heat exchanger using a water stream.
4.3 Absorber Modelling

After the hot gases of the reaction were cooled down to 150ºC with the use of the heat exchanger [X201],
the almost dry gas mixture had to be introduced in an absorption column. The absorption column used in
this reaction as also specified in section 3.3 uses water, and works in counter current mode. At this point
the greater challenge of the simulation appeared. Interaction of formaldehyde with water produces
16
April 20th, 2018
methylene glycol. This is a component which does not exist in ASPEN something that made the simulation
really challenging.
The simulation started by defining the molecular structure of methylene glycol in Aspen. The
program can use the given structure in combination with some defined methods and determine some of the
chemical and physical properties of a compound but also accept user defined parameters to be introduced.
The next step was to look for the properties which are required by ASPEN and needed for the design of our
absorption column and trying to fill these gaps using values found in literature sources.
Defining with the use of Henry’s constant seemed like a promising approach because it gives an
indication of the extent of solubility of formaldehyde in water as a function of temperature and pressure.
The equation was determined in a study found in literature, the corresponding coefficients were inputted in
ASPEN. This gave a way of modelling the behavior of methylene glycol with respect to the Henry’s
constant.
The basic idea was to actually use a reactor to produce methylene glycol and thus introduce it in
our absorption column. In order to check whether or not the user defined methylene glycol parameters were
giving the correct physical interactions, a reactor model was built up. Different reactors were used from a
plug flow to a CISTR and Stoichiometric reactor. Based on literature values17 we were checking the reactors
based on the enthalpy change with the desired value being between -20 and -40kJ/mol.
The reactors were checked both before and after defining the Henry’s constant equation.
Unfortunately, the result was not the desired one as at the beginning we were getting a positive enthalpy
change and no methylene glycol in the outlet streams and after defining the Henry’s constant we got
methylene glycol produced but an enthalpy change of around -80kJ/mol.
When we saw that the methods we already tried could not work realistically we then introduced the
enthalpy change of the hydration in the ASPEN as found in literature. Therefore, the simulation then ran
accordingly giving the agreeable enthalpy change. At first we were getting a stream out of every stage of
the absorption column feed it in a Stoichiometric reactor and then put the outlet feed containing methylene
glycol in the next. This resulted in a really complicated and confusing model and thus an alternative pathway
was tried by introducing the reaction at the specifications of the rate based radfrac block. This had also the
advantage of a far smoother simulation since ASPEN did not have to run simultaneously many reactors
which made it lag. The reaction was set as an equilibrium one, occurring at every stage of the column (from
stage 1 to stage 5). The coefficients of the equilibrium constant expression were filled in using a literature
source.18
After the methylene glycol was introduced in the absorption column, the next thing to be done was
to build the absorption column based on the model and work on its optimization. Coolers were used to
cool the streams to the temperature shown in Figure 4.4 below. It can be seen that the temperature increases
from stage 1 to stage 5 as the solubility increases with increasing temperature.
17
18
17
April 20th, 2018
Figure 4.4: Sketch of the absorption column
Table 4.4 below shows different trials of the optimization of the absorption column. The diameter of the
column and the packed height per stage were varied to see their effect and decide the dimensions of the
block.
Section Diameter (m) Packed Height per Formaldehyde weight Mass percentage of
stage (m) percentage of product formaldehyde and
(%) methylene glycol in
recovery (%)
3 2.5 43.59 3.85
5 5 43.74 3.76
10 10 43.8 3.72
2 2 43.64 3.81
2 1.5 43.31 4.03
2 2.5 43.53 3.9
4 4 43.7 3.79
Table 4.4: Influence of dimensions on the wt% formaldehyde in the product
By trying different dimensions for the design of the absorption column it was seen that the minimum section
diameter was 2 m and the minimum packed height per stage was 1.5 m. Smaller dimensions were giving
errors to the simulation. It was desired to keep the mass percentage of formaldehyde and methylene glycol
in the recovery below 5%. This was achieved for every combination of the two dimensions thus it was not
a limiting factor. From the above values it was concluded that the optimum dimensions would be a section
dimension of 2 meters with a packed height per stage of 2 meters as well. A larger absorption was giving a
higher formaldehyde weight percentage in the product, however the change was not that much to reason
the need of a much larger budget that would be required to build and run a much larger absorption column.
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April 20th, 2018
4.4 Overall Process Modelling Conclusions:
An attempt to merge both models in ASPEN was done yet unsuccessful (ASPEN lagging and crashing
continuously), therefore two separate ASPEN files remain. The first file models the production of
formaldehyde from methanol, and the second file contains the modelling of the absorber (formaldehyde
contact with water).
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5. Results and Discussion
5.1 Collaboration with other groups

The project is done in collaboration with other groups, who are modelling other production plants. In total
there are three cooperating groups: methanol production, formaldehyde production and dimethyl ether
production.
The overview of the total process is given in figure 5.1.
Figure 5.1: The block diagram of the total process, including methanol production and DME production.
The cooperation between the groups is done in two ways:
1) Using the methanol from the methanol production group

It is known that the methanol production group produces 10600 kg/hr of methanol from 11400 kg/hr of
glycerol (see figure 5.1). From this stream, 2854 kg/hr of methanol is led to the formaldehyde production
plant, and 3000 kg/hr is led to the dimethyl ether production plant. The rest of the methanol is sold to other
organizations. The 2854 kg/hr methanol to the formaldehyde production plant results in 4099 kg/hr of 44
wt% formaldehyde solution. The 3000 kg/hr methanol to the dimethyl ether production plant results in 2098
kg/hr of 99.5wt% dimethyl ether solution.
2) Using the steam from the DME production plant

In the dimethyl ether production, 2300 kg/hr of steam with a temperature of 153°C is produced. This steam
can be used in the formaldehyde production plant, since stream 106 (see Appendix A) must be heated up
from 66°C to 600°C using superheated steam. The superheated steam (stream 107) has to be of a
temperature of 800°C, therefore the steam coming from the DME production needs to be heated up to 800°C
first, before it can be used in the formaldehyde production plant.
5.2 Mass balance
In table 5.1, a total mass balance of the process is given. The mass flow of the components in the streams
given in yellow are streams going into the system and in green are stream going out of the system. It is seen
that total in = total out = 16149 kg/hr.
For clarity, in Appendix C the concerning streams are marked with blue rectangles. Note: stream 301 is not
an in- or output stream, it is a stream that remains in the system.
20
April 20th, 2018
Table 5.1: Total mass balance

Mass flow per stream (kg/hr)
101 + 102 + 312
Component 103 (FEED) 302 105 309 (PRODUCT)
FORMALDEHYDE 0 0 0 192 21
WATER 3000 3500 1259 3664 1244
METHYLENE GLYCOL 0 0 0 214 2824
HYDROGEN 0 0 0 83 0.0015
CARBON MONOXIDE 0 0 0 86 0.016
OXYGEN 1427 0 1 633 0.128
CARBON DIOXIDE 0 0 0 210 0.269
METHANOL 2854 0 275 65 8.82
NITROGEN 5368 0 1 5366 0.94
Total 12649 3500 1536 10514 4099
16149 16149
In table 5.2, a mass balance over the reactor is given. Stream 106 is the stream entering the reactor (before
heating) and stream 203 is the stream leaving the reactor. In the balance it is seen that in the reactor there
is a net consumption of oxygen and methanol, and there is a net production of formaldehyde, water,
hydrogen, carbon monoxide and carbon dioxide. This is in line with equations [1], [2] and [3] given in
section 3.2.1.
Table 5.2: Mass balance over reactor

Mass flow per stream (kg/hr)
Component 201 203

FORMALDEHYDE 0 2112
WATER 1741 2547
METHYLENE GLYCOL 0 0
HYDROGEN 0 83
CARBON MONOXIDE 0 86
OXYGEN 1426 634
CARBON DIOXIDE 0 211
METHANOL 2579 73
NITROGEN 5367 5367
Total 11113 11113
21
April 20th, 2018
5.3 Energy balance

In table 5.3, an energy balance is given. The amount of energy that is required for each block is summed
up and it can be concluded that the total process requires 5315 kW of energy. If the plant would be built in
the United States and if it would operate 24h/day, the energy costs per day are $15307 dollars19.
Table 5.3: Energy balance

Block Q (kW)
C101 2225
X101 2395
R201 -1228
R202 -390
X201 2372
X301 -11
X302 -17
X303 -26
X304 -5
Total 5315
5.4 Mass fraction of formaldehyde in Absorber
In figure 9, the mass fraction of formaldehyde in the different stages of the absorber is given. It is seen that
the vapor mass fraction of formaldehyde increases with increasing stage number. Since in Aspen stage nr.
5 is actually the first stage, the graph must be read from right to left. Therefore, the vapor fraction of
formaldehyde is decreasing with increasing actual stage number. This is reasonable since the formaldehyde
is absorbed from the vapor phase into the liquid phase.
Figure 5.4: Mass fraction of formaldehyde in the different stages of the absorber
19 https://www.rapidtables.com/calc/electric/energy-cost-calculator.html
22
April 20th, 2018
5.5 Amount of formaldehyde in streams

The calculations of the amount of formaldehyde in the product and in the off-gas stream are done in
Appendix D. The product stream contains 44wt% formaldehyde and the off-gas stream contains 3.1wt%
formaldehyde.
5.6 Conversion of methanol

The conversion of methanol is calculated in Appendix E and amounts 88%.
5.7 Handling waste streams

The purge stream from the evaporator, stream [105], consists mainly of methanol and water. Therefore this
stream can be redirected to the methanol production group to distill it and to obtain 99% methanol again.
Another option can be to redirect the stream to the inlet feed, however the total mass flow will then change
and this will result in a change of the product stream.
The off-gas stream [309] from the absorber was intended to be combusted, however the stream contains too
much water. Before the stream is going to be combusted, the water must be removed.
5.8 Further improvement

To further improve the ASPEN model, one can try to redirect stream [105] from the evaporator into the
feed again. Also, the methanol production group has a stream of 330 tonne/hr containing steam at 153°C,
5 bar and with vapor fraction 0.30. In our model, heat exchanger [X101] operates at a pressure of 1 bar. To
further improve the model, one can change the pressure of heat exchanger [X101] to 5 bar and use a part of
the steam from the methanol production group (after it is heated to 800°C). Moreover, one can model a
demister on top of the absorber to remove the water in the off-gas stream. This is necessary to make stream
[309] suitable for combustion.
23
April 20th, 2018
6. Conclusion
The simulation of producing formaldehyde from methanol was successfully done in ASPEN, however an
attempt to merge both models in ASPEN was done yet unsuccessful (ASPEN lagging and crashing
continuously) therefore two separate ASPEN files remain. The first file models the production of
formaldehyde from methanol, and the second file contains the modelling of the absorber (formaldehyde
contact with water). The final product contains 44 wt% formaldehyde, with an input of 2854 kg
methanol/hr. The off-gas stream contains 3.1wt% formaldehyde, and the total conversion of methanol is
88%. The total energy consumption was calculated to be 5315 kW, although this value could significantly
drop if we consider recovering and using the energy of the methanol-producing group. It is also safe to
conclude that this process is green assuming that methanol that is being used is produced in a green way as
well.
24
April 20th, 2018
7. Bibliography
[1] “Formaldehyde | Uses, Benefits, and Chemical Safety Facts.” ChemicalSafetyFacts.org, 3 Apr. 2018,
www.chemicalsafetyfacts.org/formaldehyde/.
[2] Sanhoob, Mohammed Ahmad, et al. Production of Formaldehyde from Methanol. 2012, Production of
Formaldehyde from Methanol.
http://faculty.kfupm.edu.sa/CHE/rshawabk/files/Production_of_Formaldehyde_from_Methanol.pdf
[3] “Formaldehyde.” Ihsmarkit.com, 1967, ihsmarkit.com/products/chemical-technology-pep-

formaldehyde-1967.html.
https://ihsmarkit.com/products/chemical-technology-pep-formaldehyde-1967.html
[4] Millar, Graeme J., and Mary Collins. “Industrial Production of Formaldehyde Using Polycrystalline
Silver Catalyst.” Industrial & Engineering Chemistry Research, vol. 56, no. 33, 2017, pp. 9247–9265.,
doi:10.1021/acs.iecr.7b02388. p. 9250
doi:10.1021/acs.iecr.7b02388. p. 9251
doi:10.1021/acs.iecr.7b02388.
[7] Britannica, The Editors of Encyclopaedia. “Dry Gas.” Encyclopædia Britannica, Encyclopædia
Britannica, Inc., 16 Dec. 2014, www.britannica.com/science/dry-gas.
[8] Winkelman, Jozef Gerhardus Maria. Absorption of Formaldehyde in Water. Absorption of

Formaldehyde in Water. Winkelman, J. G. M. (2003). Absorption of formaldehyde in water Groningen:
s.n. Page. 45 ‘Enthalpy change’
doi:10.1021/acs.iecr.7b02388. Pagg 9249 , section 3.1
[10]Millar, Graeme J., and Mary Collins. “Industrial Production of Formaldehyde Using Polycrystalline
doi:10.1021/acs.iecr.7b02388. table 2, page 9249

s.n., page 45
25
April 20th, 2018

s.n., equation 24, page 45
[13] Energy Cost Calculator, www.rapidtables.com/calc/electric/energy-cost-calculator.html.
[14] Figures 2.1, 2.2, 2.3, 3.1 and 3.2: Ullmann’s Encyclopedia of Industrial Chemistry, Section F:
“Formaldehyde”[15] Figure 3.3 “Absorber” Winkelman, Jozef Gerhardus Maria. Absorption of
Formaldehyde in Water. Absorption of Formaldehyde in Water. Winkelman, J. G. M. (2003). Absorption
of formaldehyde in water Groningen: s.n.
26
April 20th, 2018
Appendix A
The Process Flow Diagram of the Formaldehyde production process
27
April 20th, 2018
Appendix B
Calculation for conversion of methanol to formaldehyde:
𝑚𝑜𝑙𝑒 𝑓𝑙𝑜𝑤 𝑓𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑖𝑛 202 70.3421

∗ 100 = ∗ 100 = 87%
𝑚𝑜𝑙𝑒 𝑓𝑙𝑜𝑤 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑖𝑛 201 80.48923
Calculation for overall conversion of methanol:

(1 − ) ∗ 100 = ( 1 − ) ∗ 100 = 97.15%
Appendix C
Streams taken into account in mass balance of part 1 of model.
Streams taken into account in mass balance of part 2 of model.
28
April 20th, 2018
Appendix D
Weight percent of formaldehyde in product

To calculate the weight percent of formaldehyde in a stream, the following equation is used:
(𝑛𝐹 + 𝑛𝑀𝐺 ) ∗ 𝑀𝑤,𝐹

𝑤𝐹 =
𝑚𝑡𝑜𝑡𝑎𝑙
With:
WF = weight fraction of formaldehyde
NF = molar flow rate of formaldehyde (kmol/hr)
NMG = molar flow rate of methylene glycol (kmol/hr)
MW,F = molecular weight of formaldehyde (kmol/kg)
Mtotal = total mass flow rate (kg/hr)
Composition of the product stream [312]: Composition of the off-gas stream [309]:
Component Mole flow Mw Component Mole flow Mw

(kmol/hr) (kg/kmol) (kmol/hr) (kg/kmol)
FORMALDEHYDE 0.714396 30.031 FORMALDEHYDE 6.392063 30.031
WATER 69.02807 18.016 WATER 203.3921 18.016
METHYLENE 58.77758 48.04 METHYLENE GLYCOL 4.458184 48.04

GLYCOL
HYDROGEN 7.51E-04 2 HYDROGEN 4.13E+01 2
CARBON MONOXIDE 5.64E-04 28 CARBON MONOXIDE 3.06E+00 28
OXYGEN 4.01E-03 32 OXYGEN 1.98E+01 32
CARBON DIOXIDE 6.11E-03 44 CARBON DIOXIDE 4.78E+00 44
METHANOL 0.2753405 32.04 METHANOL 2.018421 32.04
NITROGEN 0.033629 28 NITROGEN 191.5484 28
Total mass flow (kg/hr) 4099 Total mass flow (kg/hr) 10514
WF 0.435867946 WF 0.030992184
29
April 20th, 2018
Appendix E
The conversion of methanol can be calculated using the equation:
𝑛𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙,102 − (𝑛𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙,312 + 𝑛𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙,309 + 𝑛𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙,105 )

𝑋𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 =
𝑛𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙,102
With:
Xmethanol = The conversion of methanol
nmethanol,102 = the molar flow of methanol in stream [102] in kmol/hr (feed stream)
nmethanol,312 = the molar flow of methanol in stream [312] in kmol/hr (product stream)
nmethanol,309 = the molar flow of methanol in stream [309] in kmol/hr (absorber off-gas stream)
nmethanol,105 = the molar flow of methanol in stream [105] in kmol/hr (purge stream evaporator)
89.072−(0.275341+2.01842+8.58722 )
𝑋𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 = 89.072
= 0.8778
30
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Process Description and ASPEN Computer Modelling of Formaldehyde

Article · April 2018

Giuliana Maria Alvarenga Cicchelli Maria Panayi

SEE PROFILE SEE PROFILE

The user has requested enhancement of the downloaded file.

BSc Chemical Engineering

Course coordinator: dr. ir. J.G.M. (Jos) Winkelman

Process Description and ASPEN Computer Modelling of Formaldehyde

Giuliana Maria Alvarenga Cicchelli S2895455

2. Literature Survey and Process Description

Table 1: Typical Operating Parameters of Formaldehyde Plant

Methanol Flow Rate 4667 kg/h

Methanol Quantity 4620 kg/h

Molar Methanol Flow Rate 144,375 mol/h

Molar Air/Methanol Ratio 1.87

Water Flow Rate 2364 kg/h

Actual Water Flow 2222 kg/h

2.1 Incomplete Conversion and Distillative recovery of Methanol6

Figure 2.1: “Incomplete Conversion and Distillative recovery of Methanol for

2.2 Formox process

Figure 2.2: “The Formox Process for Formaldehyde Production”. Where

2.3 BASF process

3. The BASF process in detail

3.2.1 Chemical Reactions in Reactor

[1] CH3OH ↔ CH2O + H2 ΔH = +12.5 kJ/mol

[2] H2 + ½ O2 → H2O ΔH = -243 kJ/mol

[3] CH3OH + ½ O2 → CH2O + H2O ΔH = -159 kJ/mol

There are also other (less relevant) reactions forming byproducts:

[4] CH2O → CO + H2 ΔH = +12.5 kJ/mol

[5] CH3OH + 3/2 O2 → CO2 + 2 H2O ΔH = -674 kJ/mol

[6] CH2O + O2 → CO2 + H2O ΔH = -519 kJ/mol

3.3.1 Technical Description of the Absorption Column

[7] CH2O + H2O ↔ CH2(OH)2 ΔH = -31.4 kJ/mol13

3.3.2 Mass Transfer and Chemical Reactions in Absorber

MG = Methylene glycol = HO-CH2-OH = WF

WF + WF ↔ WF2 + W (HO-CH2-O-CH2-OH) (dimer)

WF + WFi-1 ↔ WFi + W (general oligomer )

4. Chronological Model Building in ASPEN

The block diagram of the process is given below.

Figure 4.1: The block diagram of formaldehyde production from methanol

4.1 Gasifier Modelling

[8] CH3OH + ½ O2 → CH2O + H2O

4.2 Reactor Modelling

Reaction number Fractional conversion Of Component

Reaction number Fractional conversion Component

Mole flow in kmol/hr

4.3 Absorber Modelling

Figure 4.4: Sketch of the absorption column

Table 4.4: Influence of dimensions on the wt% formaldehyde in the product

4.4 Overall Process Modelling Conclusions:

5. Results and Discussion

5.1 Collaboration with other groups

The overview of the total process is given in figure 5.1.

The cooperation between the groups is done in two ways:

1) Using the methanol from the methanol production group

2) Using the steam from the DME production plant

5.2 Mass balance