Palacios Ganzevles, Alexander 2019-20 P

Tutor/s
Dr. José Maria Gutierrez González

Departament d’Enginyeria Química i
Química Analítica
Treball Final de Grau
Design of a Methyl Methacrylate production plant
Alexander Palacios Ganzevles

September 2020
Aquesta obra esta subjecta a la llicència de:
Reconeixement–NoComercial-SenseObraDerivada
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Even the darkest night will end and the sun will rise.
Victor Hugo
En primer lugar, quiero agradecer a mi familia por el apoyo que me han dado durante todos
estos años, así como a mi tutor Dr. José Gutierrez por su ayuda y dedicación en este trabajo.
Design of a Methyl Methacrylate production plant 6
SUMMARY i
RESUM III
1. INTRODUCTION 5
1.1. HYSTORY 5
1.2. GENERALITIES 6
1.2.1. Properties 6
1.2.2. Uses 6
1.2.3. Risks and toxicity 7
1.2.3.1. Flammability 7
1.2.3.2. Health issues 8
1.2.3.3. Storage 8
1.2.4. Environmental impact 8
2. OBJECTIVES 11
3. METHYL METHACRYLATE PROCESS SELECTION 12

3.1. ETHYLENE PROCESSES 12
3.1.1. BASF’s Process 12
3.2. PROPYLENE PROCESSES 13
3.2.1. ACH process 13
3.2.2. Mitsubishi Gas Chemical Company process 13
3.3. C-4 FRACTION PROCESSES 14
3.3.1 Direct oxidation process 14
3.3.2. Direct oxidative esterification 14
3.4. PROCESS COMPARISON 14
4. PATENT RESEARCH 17
4.1. ASAHI PROCESS 17
4.2. PATENT US028628 18
4.3. PATENT US0251301 19
4.4. PATENT US206897 19
4.5. PATENT COMPARISON 20
5. METHYL METHACRYLATE PROCESS DESIGN 21

5.1. DESIGN BASES 21
5.2. RAW MATERIALS 21
5.3. BLOCK DIAGRAM 23
5.4. PINCH ANALYSIS 26
6. PROJECT SPECIFICATIONS 35
6.1. REACTOR 35
6.1.1. Chemical reactions 35
6.1.1.1. Main reaction 35
6.1.1.2. Secondary reactions 35
6.1.2. Reactions conversión, selectivity and space-time yield 37
6.1.2.1. Conversion and selectivity 37
6.1.2.2. Space-time yield 37
6.1.3. Operation mode 37
6.1.4. Patent requirements 38
6.1.5. Heat of the reactions 39
6.1.6. Reactor selection 40
6.1.7 Reactor design 40
6.1.8. Catalyst type, dimensions and voidage 42
6.1.9. Reactor volume 45
6.1.10. Reactor tubes 46
6.1.11. Reactor shell 46
6.1.12. Reactor baffles 47
6.1.13. Reactor materials 48
6.1.14. Reactor couplings 48
6.2. PUMPS, FANS AND COMPRESSOR 48
6.3. GAS-LIQUID SEPARATORS 49
6.4. MIXER AND PH ADJUSTMENT TANK 50
6.5. STORAGE TANKS 50
6.6. HEAT EXCHANGERS 51
6.7. PIPING 52
6.8. INDUSTRIAL SERVICES 53
7. CONCLUSIONS 55
REFERENCES AND NOTES 57
ACRONYMS 59
APPENDICES 61
APPENDIX 1: MASS BALANCE 64
APPENDIX 2: ENERGY BALANCE 70
APPENDIX 3: PINCH ANALYSIS 78
APPENDIX 4: REACTOR DESIGN 79
APPENDIX 5: EQUIPMENT DESIGN 86

Design of a Methyl Methacrylate production plant i
1. SUMMARY
Methyl methacrylate is a monomer which is majority used to produce polymethyl methacrylate
which has a wide range of applications due to his transparency, weather-resistance, and stability.
Moreover, it is used to make methacrylate resins for coatings and inks.
Due to its importance, a great number of processes to obtain it has been developed, which
are reliant on the different raw materials employed due to the expected location of the plant.
In this work it has been selected a process to produce methyl methacrylate from methacrolein
as it has the advantage that is an intermediate that can be obtained from two of the three raw
materials commonly used. Afterwards, it has been searched for improvements over it in patents
to avoid inconveniences caused by the secondary by-products; and to increase the productivity.
Finally, it is carried out the reactor selection and design, as well as the other equipment needed
for its properly operation.
The plant design has been done without limitations when it comes to raw materials, services
or energy needed and to achieve a production of 40.000 tones / year; the product would require
a final purification so that it can be commercialised that is not included in the scope of this project.
Keywords: Methyl methacrylate, manufacturing process, equipment design, patents

Design of a Methyl Methacrylate production plant ii
Design of a Methyl Methacrylate production plant iii
2. RESUM
El metacrilato de metilo es un monómero que se utiliza mayoritariamente para producir
polimetacrilato de metilo, el cual tiene una amplia variedad de aplicaciones debido a su
transparencia, resistencia a la intemperie y estabilidad. Además, se utiliza para fabricar resinas
de metacrilato para revestimientos y tintas.
Debido a su importancia, se ha desarrollado varios procesos para su obtención, que
dependen de las diferentes materias primas empleadas debido a la ubicación prevista de la
planta.
En este trabajo se ha seleccionado un proceso para producir metacrilato de metilo a partir de
metacroleína, ya que tiene la ventaja de que es un intermediario que se puede obtener a partir
de dos de las tres materias primas utilizadas. Posteriormente, se ha realizado un estudio de las
diversas patentes para tener en cuenta las mejoras del proceso y así evitar inconvenientes en su
operación, puesto que se forman productos secundarios; y también para aumentar la
productividad. Finalmente se ha realizado la selección y diseño del reactor, así como del resto
de equipos necesarios para alcanzar una producción de 40.000 toneladas/año. El producto
obtenido requerirá de una purificación final para poder ser comercializado, la cual no está en el
alcance de este proyecto.
Palabras clave: Metacrilato de metilo, proceso de producción, diseño de equipos, patentes.

Design of a Methyl Methacrylate production plant iv
1. INTRODUCTION
Methyl methacrylate is an organic compound which is used to produce polymer-based
products such as acrylic glass, coatings and inks. In addition, it is considered as the most
important methacrylic ester due to his usability as a raw material for the manufacture of
methacrylate derivatives.
That is why it is interesting to be able to produce methyl methacrylate in an economic way
and as simple as possible. Due to the high consumption of methyl methacrylate, it has been
chosen to design a continuous methyl methacrylate production plant.
1.1. HYSTORY
In historical terms, in 1843 the acrylic acid was synthesized for first time. Nearly twenty years
later, the methacrylic acid was formulated from it. This fact was an important step to its creation,
since methacrylic acid, along with methanol, react producing ester methyl methacrylate, the single
chemical compound from which other methacrylates are created.
In the early 1930s, British chemists Rowland Hill and John Crawford discovered polymethyl
methacrylate at Imperial Chemical Industries (ICI) in the United Kingdom. The product was
registered under the trademark Perspex.
At the same time, German chemist and industrialist Otto Röhm and Haas AG produced safety
glass by polymerizing methyl methacrylate between two layers of glass. The polymer separated
from the glass was trademarked as Plexiglass in 1933 (GmbH, 2020). So, both Perspex and
Plexiglass were commercialized in the late 1930s.
In the United States, the DuPont Company introduced its own product named Lucite. The
Lucite International was the first company in commercialising viable production of acrylic safety
glass.
Moreover, during World War II, both sides used methyl methacrylate to create submarine
periscopes, aircraft windshields and gun turrets. In fact, the airplane pilots whose eyes were
injured by PMMA shreds healed much better than those damaged by standard glass.
6 Design of a Methyl Methacrylate production plant
Nowadays, methyl methacrylate is present in our lives. It is used to produce polymethyl

methacrylate and so prove of this omnipresence, is the still popularity of trademarks like Plexiglas,
Perspex o Lucite, being Plexiglas the least known in Spain.
1.2. GENERALITIES
1.2.1. Properties
Methyl methacrylate, also known as methyl 2-methylpropeonate according to IUPAC, has the
chemical formula C5H8O2 and the molecular weight of 100.121 g/mol. It is characterized of being
a colourless, toxic and a flammable liquid.
Methyl methacrylate appears as a clear colourless volatile liquid. It is slightly soluble and floats
on water and its vapours are heavier than air. Its odour is a characteristic quality is sulphur-like,
sweet and sharp. Its hedonic tone results unpleasant for living beings; and it is also acrid and
fruity.
Regarding its main properties, are as follows:
Table 1: Main properties of methyl methacrylate

Ionization Potential (eV) 9.70
Boiling Point (ºC) 101
Melting Point (ºC) -48
Critic Temperature (ºC) 291
Autoignition Temperature (ºC) 435
Viscosity at 24ºC (mPa·s) 0.53
Vapor pressure at 25ªC 3.87
Specific gravity 0.939
1.2.2. Uses
Thanks to its acrid and fruity odour it is been used as a food additive and flavouring agent,
and it also has organoleptic properties, as an aromatic, acrylic and fruity flavour.
As well, methyl methacrylate is a reactive resin, and the polymerized form is used as cement
in dentistry, orthopaedic surgery and ophthalmology (Dunne, Clements, & Wang, 2014). The
monomer form has relaxation effect on smooth muscle and it might be due to the nitric oxide-
mediated response.
It is also used in the manufacture of methacrylate resins and plastics (example: Plexiglas,
Lucite). The principal uses are cast sheet (advertising signs, building panels and sidings, lighting
fixtures, skylights and glazing…), moulding/extrusion powder and coatings (lacquer, latex paints
and enamel resins).
Nowadays, the largest application for methyl methacrylate (80%) is to produce polymethyl
methacrylate, which resins are employed to make products that require good optical clarity,
weather-resistance, and stability. Its major use is in surface coatings, generally emulsion
polymers for architectural and maintenance paints.
In less proportion, it is also used to produce copolymers such as methyl methacrylate-
butadiene-styrene, which its resins are used as a modifier for clear rigid PVC and in food and
pharmaceutical packaging.
In Asia, they are new applications related to transparent acrylonitrile-butadiene-styrene resins
that are used in computer casings and mobile phones.
1.2.3. Risks and toxicity

Methyl methacrylate is included in Special Health Hazard Substance List because of its
flammable and reactive properties, so its risks and possible damages have to be taken into
account.
1.2.3.1. Flammability
In terms of flammability, it is considered, according to the National Fire Protection Association
(NFPA), a material belonging to Class IB Flammable Liquid: the flash point is below 22.8ºC (73ºF)
and the boiling point at or above 37.8ºC (100ºF); and so is regarded as severe risk.
In case it provokes a fire, it produces toxic gases and containers can explode. Due to its
properties, water is not efficient to this kind of explosions, so it must be used chemical substances
like carbon dioxide, alcohol resistant foam or another foam agent so that it is in inert conditions.
1.2.3.2. Health issues

The methyl methacrylate exposure can cause short-term or long-term health effects.
In short-term effects, methyl methacrylate contact irritates the eyes, skin, nose and throat.
Inhaling it can also irritate lungs and provoke coughing and trouble breathing. At higher levels,
exposure can cause a liquid accumulation in lungs (pulmonary edema), a medical emergency
that has to be attended immediately.
The long-term effects can take months or years. There is the possibility of cancer risk and
sterility. It can also cause skin allergy, liver and kidney injuries and cause damage to the nervous
system.
Good work practices can help to reduce dangerous exposures. It is recommended to the
workers to change the clothing that has been contaminated by methyl methacrylate and to provide
eye wash fountains in case of emergency use. Another recommended also stated is to wear
protective gloves and clothing material, resistant googles and face shield when it is being
manipulated.
Improper use of respirators is dangerous; such equipment should only be used if the
workplace conditions require it (exposure over 50 ppm, considering that if it is higher than 1000 it
is extremely hazardous).
1.2.3.3. Storage
It also has incompatibilities with nitrates, oxidizers, peroxides, strong alkalis, and moisture.
Moreover, it may polymerize if it is subjected to heat, oxidizers or ultraviolet light.
Therefore, in terms of handling and storage, the methyl methacrylate has to be stored in tightly
closed containers in a cool, well-ventilated area so that it is away from the conditions
aforementioned before.
1.2.4. Environmental impact

Methyl methacrylate is not known to occur naturally, as it is industrially manufactured and
used within closed systems. It can enter the environment during its storage, transport and use,
potentially via wastewater and exhaust gases. Emissions to water, air and soil from production
plants are about 0.46%; and most of it (98%) is emitted to air.
It is not used to persist in the environment due to its faster biodegradation in sewage treatment
plants. It is also unlikely to bind to soil because of its low adsorption coefficient; and if it is released
to atmosphere, it is degraded in a few days. Neither it is expected to accumulate in food.
It should be noted that upon short-term exposure on living beings, methyl methacrylate is
dangerous to fish and invertebrates but not algae. On the contrary, it is not harmful to aquatic
organisms upon long-term exposure.
2. OBJECTIVES
The main aim of this Final Degree Project is to design a plant in continuous to produce 40.000
tons of methyl methacrylate per year. With the purpose to achieve it, the followed tasks will be
done:
- To carry out the selection of the process to produce methyl methacrylate in a short
pathway and based on different first raw materials.
- To do a bibliographical research to find improvements that has been made over the
process to increase the productivity.
- To do the basic engineering of the process according to the improvements founded over
it.
- To select and design the reactor, as well as the other equipment required to accomplish
the production demand.
3. METHYL METHACRYLATE PROCESS SELECTION

As stated in the bibliography, a wide variety of processes to manufacture methyl methacrylate
have been developed on the basis of the different raw materials available in the respective
locations, where it is desired to build the plant, and some of them were commercialised in
industrial scale. In addition, some improvements have been carried out over time in some of the
processes designed in order to reduce costs, improve the yield and conversion and to avoid
producing some undesired products. These methods continue to be based on natural gas or crude
oil, so that the manufacturing routes to produce it are categorized according to the hydrocarbon
raw materials.
3.1. ETHYLENE PROCESSES

Methyl methacrylate can be manufactured on ethylene basis by different ways, whether the
intermediate is propionaldehyde, propionic acid or methyl propionate. One of the process
developed, called the Alpha process, allows to produce the methacrylic ester with methyl
propionate as the intermediate. However, as with propionic acid, this process suffers from low
conversion, despite the selectivity is high. It would be needed to implement large recycle streams
or an improvement over the catalyst.
3.1.1. BASF’s process

BASF developed a C-2 process where methyl methacrylate is produced by ethylene and
where the intermediate is propionaldehyde (Ullmann, 2011). On the first step, propionaldehyde is
produced by a hydroformylation process where ethylene reacts with syngas using rhodium
catalyst. Then, propionaldehyde reacts with formaldehyde in liquid phase to produce
methacrolein. This last reaction is catalysed by a secondary amine and an acid to improve the
conversion.
Once the methacrolein is provided, it is oxidized by air over a catalyst composed by
molybdenum and tungsten, among others, to produce methacrylic acid. In the last step, the
esterification of methacrylic acid with methanol is carried out to obtain methyl methacrylate. BASF
operates a plant in Germany based on this process.
3.2. PROPYLENE PROCESSES
3.2.1. ACH process

The main worldwide pathway to produce methyl methacrylate continues being the acetone
cyanohydrin process (Ullmann, 2011), which is the first process industrialized. By this process,
acetone and hydrogen cyanide are first reacted to give acetone cyanohydrin. Afterwards, acetone
cyanohydrin reacts with sulphuric acid, that has been added in excess, to produce α-
sulphatoisobutyramide which, under heated conditions, gives methacrylamide sulphate. On a final
stage, the hydrolysis-esterification of methacrylamide sulphate with methanol, using sulphuric
acid as a catalyst, gives methyl methacrylate, methacrylic acid and ammonium bisulphate.
The main drawback of this process is the high costs of waste treatment since nearly 1,5 tons
of ammonium bisulphate are produced for every ton of methyl methacrylate. Other disadvantages
are the need of supply hydrogen cyanide and the cost and corrosivity of sulphuric acid.
3.2.2. Mitsubishi Gas Chemical Company process

This process was intended to improve the acetone cyanohydrin process with the aim of not
using sulphuric acid and to cut down on the waste handling (Kirk & Othmer, 2005).
Firstly, the acetone cyanohydrin is produced as in the ACH process, which is hydrated to
obtain α-hydroxy isobutylamide using manganese catalyst. Once produced, it is esterified by
methylformate to produce methyl α-hydroxy isobutylate. Finally, it is dehydrated to provide methyl
methacrylate. This process produces formaldehyde as a by-product instead of producing
ammonium bisulphate. The formaldehyde is dehydrated with the aim of produce hydrogen
cyanide, which is recycled.
Other routes based on 3 carbon hydrocarbons are mainly those that allow to obtain the
methacrylic ester from propyne or isobutyric acid. It has been developed a single-step process
but seems to be unavailable in an industrial scale due to the amount of propyne required. On the
other hand, it is needed to improve the catalyst to be economically viable the industrialization of
the isobutyric acid route (Kirk & Othmer, 2005).
3.3. C-4 FRACTION PROCESSES

In case of C-4 processes, some of them are directly discarded in this selection due to their
disadvantages. These are the Escambia process due to the large amount of nitric acid required
to be handled (Nagai, 2001); the methacrylonitrile route due to the ammonium bisulphate waste
(Nagai & Ui, Trends and Future of Monomer-MMA Technologies, 2004) and the isobutane direct
oxidation process due to the large number of reaction steps (Kirk & Othmer, 2005).
3.3.1. Direct oxidation process

Methyl methacrylate can also be manufactured using isobutylene or tert-butanol as raw
materials (Nagai & Ui, Trends and Future of Monomer-MMA Technologies, 2004). In this case,
isobutylene or tert-butanol first are oxidized with air to produce methacrolein, with allows to obtain
methyl methacrylate by the same way that has explained in the BASF process. There are some
variations of this route depending on whether the methacrolein is separated from the effluent of
the first reactor or if it is directly introduced in the second reactor.
3.3.2. Direct oxidative esterification process

It has been carried out process intensification by Asahi Kasei in order to reduce the steps
required to manufacture methyl methacrylate by two (Nagai & Ui, Trends and Future of Monomer-
MMA Technologies, 2004). Through this process, first methacrolein is produced by isobutylene
as a raw material in the same way as the direct oxidation process. In contrast, in the next step is
carried out an oxidative esterification reaction where methacrolein and methanol reacts in liquid
phase with oxygen in gas phase to produce the desired methacrylic ester.
3.4. PROCESS COMPARISON

One of the most important aspects to consider when it comes to select the process is the raw
materials location and costs, as this will determine the overall cost of the plant that is going to be
designed. Once taken into account all the processes mentioned, the Mitsubishi Gas Chemical
company process it is discarded due to the long pathway that it presents. The direct oxidative
esterification process not only allows to manufacture methyl methacrylate in a shorter pathway,
but also is flexible in terms of raw materials due to the fact that methacrolein can be produced by
ethylene, isobutylene or tert-butanol with both the BASF or the direct oxidation process. In
addition, the direct oxidative esterification process does not produce ammonium bisulphate,
avoiding issues regarding to its waste management. For these reasons commented, the direct
oxidative esterification process has been chosen to design the methyl methacrylate plant from
methacrolein.
4. PATENT RESEARCH
Once selected the process, it has been searched for the carried out by Asahi, as well as for
patents that stated new developments over the direct oxidative esterification to carry out the
process design. The ones selected are those indicated above.
4.1. ASAHI PROCESS

The direct oxidative esterification process developed by Asahi was commercialised in an
industrial scale employing a stirred tank reactor. According to a recent publication (Liang et. al.,
2019), the reactor operates at 50ºC of temperature and 1 bar, and the conversion and selectivity
to obtain methyl methacrylate are respectively 98.8% and 85.9%. The liquid phase effluent of the
reactor is separated from the gas phase in a gas-liquid separator and it is fed to a distillation
column. Afterwards, the methanol and methacrolein recovered from the top of the distillation
column are recycled to the reactor whilst the liquid phase of the bottom of the distillation column
is sent to the purification stages to obtain methyl methacrylate with high purity.
However, a selectivity in a range of from 80% to 85% approximately is still unsatisfactorily for
being commercialised (US patent 6,040,472) as the secondary reactions produce by-products
such as methyl formate, carbon dioxide and water, which difficult the final separation and
purification of the methyl methacrylate. Moreover, the polymerization reactions of methacrolein
must be avoided because it causes obstruction and deactivation of the catalyst (US patent
0,280,620).
It has also been stated that when it is tried to reduce the amount of methanol in excess to
increase the productivity, the yield decreases. Another disadvantage of the process is that
recycling the excess of methanol and the separation of the by-products requires a lot of energy
(Nagai & Ui, Trends and Future of Monomer-MMA Technologies, 2004). For these reasons, it has
been searched in patents for improvements that have been made on the reactor before doing the
process design.
During the research, it that has been found patents that informs about new catalyst developed
that reduce the selectivity of some of the secondary reactions. These patents have not been
preselected as the main criteria that has been decided is to consider those that provides
experimental results of the reactor applying the new catalyst innovated. The final selection will be
made considering the conversion and selectivity of the reactor, as well as the operation conditions
and the reactor type.
4.2. PATENT US0280628

This patent claims that it has been achieved a conversion and selectivity to methyl
methacrylate up to 69.8% and 97.2% respectively in a long period of time employing a tubular
reactor in a laboratory scale. It is stated that, to reach these values, it is necessary that the
concentration of methacrolein in the reactor is always equal or less than 15% and the ratio
between the liquid volume in litres and the catalyst weight in the reactor in kilograms is equal or
less than 4.
In the process proposed in this patent, firstly the liquid stream of methanol and methacrolein
is mixed with a gas stream of oxygen and nitrogen previous feeding it into the catalytic reactor at
6 bars. The gas stream that enters the reactor has a concentration of 7% in volume of oxygen to
avoid explosive atmospheres in the reactor, whereas the liquid steam that enters the reactor is
stoichiometrically in excess of methanol.
The reactor operates with an external heat exchanger to maintain the temperature at 80ºC.
The output stream of the reactor is then cooled with a heat exchanger and, afterwards, the gas
phase is separated from the liquid phase in a gas-liquid separator. The liquid phase remained is
then conveyed to a neutralization tank to adjust the pH at a value of 7. Finally, the methyl
methacrylate is withdrawn to a further purification and the remaining liquid phase is recirculated
to the reactor.
This patent does not specify neither how to detach the methyl methacrylate from the rest of
the liquid products of the reactor, nor the temperature of the stream that enters the reactor and at
which temperature is cooled the stream that leaves it. Moreover, and the conversion is lower than
in the Asahi process. Despite of that facts, the main advantages are the high selectivity and the
fact that the reactions take place in a tubular reactor. In industrial scale, it would be used a multi-
tubular reactor, which has a large surface area to exchange the heat generated.
4.3. PATENT US0251301

This patent has similarities with the previous commented as far as the process is concerned
and also the conversion and selectivity achieved are the same, whereas it is used another
catalyst, the feed enters the reactor at 11 bars and the temperature of the tubular reactor is
maintained at 70ºC.
The patent specifies the importance of maintaining the pH at least between 5 and 9. In case
that it is higher, it would be harmful for the stability of the catalyst. On the other hand, if the pH is
lower than indicated, secondary reactions would be favoured causing the formation of the
by-product 1,1-dimethoxyisobutene, which would lead to a reduction of the yield and the stability
of the catalyst and also would complicate the separation of the final product.
However, it is stated that the liquid phase stream that leaves the gas-liquid separator, after
being adjusted its pH in the neutralisation tank, it is recirculated to the reactor at least the 50% of
it, preferably the 90%. That recirculation is carried out with the aim that there is a great deal of
liquid in the reactor, increasing the amount of oxygen that is dissolved in it and in contact with the
catalyst. This might be beneficial to achieve the conversion indicated, but has the disadvantage
that the methyl methacrylate produced is also recirculated in that high percentage to the entrance
of the reactor, instead of being withdrawn and purified to obtain it as the final product, which
significantly decreases the productivity of the overall process.
4.4. PATENT US0206897

This patent provides a pathway to produce methyl methacrylate from ethylene. Since the
objective is to design a process where methacrolein can be produced by ethylene, this patent has
also been taken into consideration for the process design. It would be needed three reactors to
produce methyl methacrylate according to it, as previously it must be produced the
propionaldehyde and methacrolein. However, it has been focused on the last reactor of the
pathway as it is the one of interest in this project.
As it is stated, the methacrolein produced must be separated from the other products of the
second reactor before being fed to the last reactor with oxygen and methanol in slight excess.
The reactor employed to produce methyl methacrylate is a slurry stirred tank reactor as the
oxygen is bubbled through it and the catalyst is suspended in the liquid. Once the reaction take
place at 50ºC and at atmospheric pressure, the products leaves the reactor with the catalyst. To
obtain methyl methacrylate in high concentration, the patent proposes that first it is separated
from the catalyst by filtering, and then it is separated from the by-products by distillation.
The main drawback of the patent is that the conversion of methacrolein and selectivity to
produce methyl methacrylate are 50% and 90%, values lower than in the Asahi process. Another
disadvantage is that, as the catalyst is not fixed in the reactor like in a fixed bed, it must be also
supplied with the reactants and separated from the products. In addition, the stirred reactor tank
would also require an external heat exchanger, but the surface area would be limited.
4.5. PATENT COMPARISON

After taking into consideration all patents mentioned above, it has been inclined to the reactor
of patent US0280628 as the best option because, despite the fact that the conversion is lower
than in the original process considered, the selectivity is higher and the reactor type eases the
withdraw of the reactions heat. In addition, the reactor operates at a higher temperature and at a
lower pressure in comparison with ones in the patent US0251301, which means that it would be
needed to withdraw less amount of the heat generated; and also that the power required to be
provided by the pumps and fans previous the reactor will be lower.
The patent US0206897 is going to be considered when it comes to employ the methacrolein
that is obtained from an ethylene process, but the reactor proposed is discarded due to the reactor
type and low yield. The Asahi process reactor works at the same temperature and pressure as
the reactor commented in this patent, but the yield is lower in the latter case. That is related to
the fact that, when methanol is not at sufficient excess, both the conversion and the selectivity
tend to lessen (US patent 5,969,178).
5. METHYL METHACRYLATE PROCESS DESIGN

5.1. DESIGN BASES
The main objective of this project is to design a methyl methacrylate plant from methacrolein
operating in continuous mode that accomplishes the demands of producing 40.000 tons per year.
The plant is going to be designed operating 8.000 hours / year. No limitations have been
considered in terms of the amount of resources, energy and raw materials needed.
The process will be designed considering the secondary reactions that causes the formation
of carbon dioxide and methyl formate, and its separation from the methyl methacrylate and other
by-products. Contrary to the Asahi process, in the patent selected is commented that during the
experiments there was no obstruction in the tubes because the polymeric by-products were not
formed, so they have not been considered. Other by-products are formed such as methacrylic
acid, but as the selectivity of the main reaction is very high and these do not influence the reactor
and the process design, they have neither taken into account.
The final product would need a further purification to obtain it at a concentration of 99,9% for
being commercialised. That final separation will not be in the scope of in this project, as it will be
focused on the design of the methyl methacrylate reactor and the auxiliary equipment needed for
the reactor operation.
5.2. RAW MATERIALS

Before carrying out the process design, firstly it is going to select the raw materials that are
available in the market and the methacrolein employed whether it is produced from ethylene or
isobutylene.
In the case where methacrolein is obtained from isobutylene by the Asahi process, it is
separated with high purity in an absorption column employing methanol as absorbent (Liang et.
al., 2019). That would be beneficial for our process design as it can be considered that only
methanol is withdrawn by the stream of methanol; and because the absorbent is also a reactant,
so that it has not to be treated as an impurity.
However, in a study carried out to determine the relationship between the amount of
methacrolein obtained and the flow rate of methanol fed in the absorption column, it has been
stated that the preferred methanol flow rate is 3000 kmol/h to obtain approximately 74.5 kmol/h
of methacrolein (Liang et. al., 2019). If the flow rate of methanol is lower, it would be constantly
wasted part of the methacrolein produced. Otherwise, when the methanol flow rate is higher, the
extra amount of methacrolein that can be obtained gradually decreases and there is no point in
increasing the absorbent flow rate up to this value as it does not compensate the costs associated.
Considering that the inlet stream of methanol to the absorption column has the flow rate
mentioned, the output stream of interest will have a concentration of 5% in mass of methacrolein
approximately, which means that the excess of methanol is way higher than the indicated in the
patent. It would be needed to reduce the amount of methanol to achieve the operation conditions
stated in the patent.
On the other hand, the methacrolein can be obtained from ethylene with propionaldehyde as
the intermediate, which reacts with formaldehyde in presence of a secondary amine and an
organic acid. By this way, an aqueous and an organic phase are formed after cooling the reaction
mixture produced. The organic phase contains a 90% of methacrolein, which can be separated
from the other products by distillation (US patent 0,206,897).
In this project, the methacrolein considered is that obtained from ethylene because it requires
an addition of methanol in the process and it is assumed that have impurities. As no information
about the methacrolein obtained by this way has been found, it has assumed that the
propionaldehyde is the main impurity and that methacrolein has a purity of 99.9%, as it is available
in the market in that concentration and that it is at 25ºC. The process that is going to be designed
would also be valid for the other case if the excess of methanol is reduced.
Therefore, the following raw materials and supplies are needed in the process:
• Methacrolein, which will be supplied with a concentration of 99.9% with propionaldehyde.
• As commented in the patent, the oxygen will be fed to the reactor in a concentration of
7% with nitrogen.
• The reaction will take place with excess of methanol, which will be supplied with a purity
of 99.9% with water.
• To adjust the pH, it will be employed sodium hydroxide at a concentration of 50% with
water. It is stated in the patent that it is fed a solution of sodium hydroxide at 1% with methanol
and, as no information has been found about the amount of it that is needed, it has maintained
that proportion for the feeding to the mixing tank.
• It is not expected that the pH increases over the maximum value of 6.5 but in case that it
happened, sulphuric acid at a concentration of 98% will be fed to adjust it.
5.3. BLOCK DIAGRAM

Once it is known the raw materials that are going to be employed, the production process is
being designed considering the proposition of the patent, but some changes have been made
over it.
At first, it was suggested that a neutralisation tank is placed to adjust only the pH of the
recirculated stream, which then is combined with all the raw materials streams. Instead of that, it
has been decided that the methacrolein, methanol and the sodium hydroxide streams are also
fed to a mixing tank to ensure that the pH of the liquid phase of the stream that enters the reactor
is between the optimum range. In it, the will be a homogenization of the streams, the pH will be
adjusted, and the temperature will be increased up to a value of 51ºC, taking advantage of the
fact that the recycling stream is at a temperature of 63ºC.
Due to the heat provided by the recirculation stream in the mixing tank, the propionaldehyde
switches to gas phase. It is removed after the mixing tank in a gas - liquid separator as it is an
impurity and to avoid issues when it comes to pump the liquid phase remaining.
The output liquid stream of the gas - liquid separator is then heated to reach a temperature of
60ºC. At the same time, the gas stream of oxygen and nitrogen is compressed and heated to the
same temperature. Both streams are then combined and fed to the catalytic reactor.
The products that leaves the reactor are not going to be cooled previous separating both
phases formed as indicated in the patent. This decision has been made because, as the reactor
is cooled so that the maximum temperature on it is of 80ºC, the methacrolein and methanol that
have not reacted leaves the reactor at gas phase, amongst others, whereas the methyl
methacrylate and water were at liquid phase. If it is cooled so that these raw materials are
condensed then, after separating the gas phase remaining, it would be needed to be distilled to
separate them from the water and methyl methacrylate. That would imply more costs as it would
be needed an extra equipment and to provide more industrial services not only to condense those
raw materials, but also to vaporize them again.
Finally, after separating the liquid phase that leaves the reactor, it is cooled and stored as the
final product of the process. The gas phase withdrawn is cooled at a temperature of 63ºC to
assure the condensation of methanol and methacrolein. These compounds are then separated
from the gas phase remaining and recirculated to the mixing tank. By this way, these raw materials
are reused as they react in liquid phase and the by-products methyl formate and carbon dioxide,
amongst others, are eliminated, avoiding the need of a purging stream that withdraw a fraction of
the raw materials recirculated.
A block diagram is shown hereafter, where it is represented the stages of the process, as well
as the raw materials to provide in it and the residual gases that are withdrawn.
Figure 1: Process Blog Diagram

5.4. PINCH ANALYSIS

There are streams in the process designed that requires an exchange of heat, which entails
costs due to the supply of hot and cold services. To reduce the energy consumption in services,
a pinch analysis has been made over the process. In this analysis, the heat that need to be
withdrawn from the reactor is not included as it will be cooled with cold services to ensure its
properly operation. Therefore, the streams that requires an exchange of heat that are considered
in the analysis, are as follows:
• Liquid phase stream inlet to reactor.
• Oxygen and nitrogen stream inlet to reactor.
• Recirculating stream.
• Methyl methacrylate stream to storage tank.
The first two are cold streams which must be heated whereas the other two are hot streams
that must be cooled. The results obtained are shown below:
Table 2: Pinch Analysis results

Pinch point -
Minimum cooling by services (kW) 3524
Minimum heating by services (kW) 0
According to the results obtained, no heating services are needed and there is no pinch point.
That is because a great amount of heat needs to be cooled in the recirculating stream, mainly
due to the condensation of methacrolein and methanol. These results are obtained from the
following graphs.
90
80
70
Temperature (°C)
60
50 Cold compound
curve
40
30
20
10
0
0 600 1200 1800 2400 3000 3600
Heat (kW)
The cold and hot compounds curves are first carried out:
Figure 2: Hot and cold compound curves
The compound curves are then displaced to ensure a minimum variation of temperature of
20ºC between the curves so that the heat exchangers to design are not of high dimensions,
despite that it requires more services than if it were lower.
90
80
70
Temperature (°C)
60
50 Cold compound
curve
40
30
20
10
0
0 600 1200 1800 2400 3000 3600
Heat (kW)
Figure 3: Compound curves displaced

In the previous graph can be determined the minimum cold services. In addition, it is observed
that there are no minimum hot services. In the following graph it can also be found that information
and the inexistence of the pinch point.
Figure 4: Grand compound curves
Due to the results obtained, the heat exchange network diagram has been done without the
pinch point and verifying that the minimum variation of temperature of 20ºC is accomplish in all
the heat exchangers between the streams that enter or leaves it in the same size. Is can be seen
in it the heat exchangers proposed to exchange heat between the streams and the heat
exchangers that provides cold services to achieve the final temperature desired.
Figure 5: Heat exchange network diagram

It has only been reduced the energy to exchange by a 7%. As it can be observed it is needed
a heat exchanger for cooling services and another for heating services.
Therefore, the heat exchangers that are needed in the process according to the Pinch
Analysis are as follows:
• H.E.01, were the liquid phase inlet to reactor tubes side is heated to 60ºC employing the
recycling stream.
• H.E.03, were the oxygen and nitrogen inlet to reactor is heated to 55ºC employing the
methyl methacrylate final stream.
• H.E.04 were the oxygen and nitrogen inlet to reactor is heated to 60ºC employing hot
services.
• H.E.05, were the methyl methacrylate stream is cooled to 30ºC employing cold services.
• H.E.06, were the recirculating stream is cooled to 63ºC employing cold services.
Once the Pinch Analysis is done, it can be detected that one more heat exchanger is needed
to heat the gas stream that enters to the reactor (H.E.02) and that the heat exchanger previously
commented to provides heat services (H.E.04) is going to be oversized. That is because, if it is
not present, the reactants streams are not heated in the start-up of the plant as the recycling and
the methyl methacrylate streams does not flow towards the heat exchangers yet. Also, these are
useful to ensure that the raw materials stream achieves the temperature required for the reactor
operation.
Figure 6: Process Flow Diagram previous applying the Pinch Analysis

Table 3: Mass Balance

Figure 6: Process Flow Diagram after applying the Pinch Analysis

6. PROJECT SPECIFICATIONS
6.1. REACTOR
The multiphasic reactor is the most important equipment to design as the methyl methacrylate
productivity depends directly on its performance. It has been studied the reactions that took place
in the reactor, as well as the heat that must be removed and the operation conditions to select
the reactor type and subsequently carry out its design.
6.1.1. Chemical reactions
6.1.1.1. Main reaction

The reaction to produce methyl methacrylate by direct oxidative esterification is at follows:
Figure 8: Oxidative esterification reaction of methacrolein
The methacrolein and methanol reacts in liquid phase with oxygen gas to generate methyl
methacrylate and water, both in liquid phase. A solid catalyst is used for the reaction, which is
carried out at 6 bar and at a temperature range between 60ºC and 80ºC.
6.1.1.2. Secondary reactions

The secondary reactions are carried out at the same pressure and temperature indicated
before, as they occur simultaneously with the main reaction. As stated before, the secondary
reactions considered are those that form methyl formate and carbon dioxide.
Methyl formate in industrial scale is produced by the carbonylation of methanol in presence
of a strong base (Ullmann, 2011). By this equilibrium reaction, methanol reacts in liquid phase
with carbon monoxide in gas phase to obtain methyl formate, also in gas phase. The concentration
that can be obtained of methyl formate decreases with temperature and increases with pressure.
In this case, the basic chemical compound that is present in the reaction mixture is the sodium
hydroxide used in the mixing tank to increase the pH.
According to the US Patent 6,168,072, when the direct oxidative esterification to produce
methyl methacrylate is carried out, methanol also reacts with oxygen to generate two moles of
water per mole of methyl formate. Therefore, the carbon monoxide is formed due to the
incomplete combustion of methanol in gas phase.
Figure 9: Incomplete combustion of methanol
Figure 10: Carbonylation of methanol
Carbon dioxide is another by-product formed by the combustion of methanol with oxygen,
both in gas phase, which also generates water. The water formed in the reactions will be in liquid
phase due to the temperature of operation.
Figure 11: Complete combustion of methanol
It is not only the main reaction, but also the secondary ones considered that are exothermic so
there will be a heat of reactions implied.
6.1.2. Reactions conversion, selectivity and space-time yield
6.1.2.1. Conversion and selectivity

According to the patent selected, after 73 hours operating the reactor carried out in laboratory
scale, the conversion of methacrolein and its selectivity for the formation of methyl methacrylate
were 70.8% and 97.4% respectively; and after 512 hours the values of these parameters were
69.8% and 97.2% respectively. It is observed a very slight decrease with time so that the latter
values mentioned can be considered constant. Therefore, the conversion of methacrolein and
selectivity for the formation of methyl methacrylate that are taken into account are 69.8% and
97.2% respectively, as the plant will operate in continuous in large periods of time.
In case of the secondary reactions, as no information is provided, it is considered that the
selectivity for the formation of methyl formate is equal to the selectivity of the formation of carbon
dioxide.
6.1.2.2. Space-time yield

The space-time yield is defined as 4.06 mole of methyl methacrylate formed per kilogram of
catalyst in the reactor and hour, as stated in the patent when the conversion and selectivity are
those indicated above.
6.1.3. Operation mode

The reactor can be differentiated whether it operates in adiabatic or nonadiabatic. The
adiabatic operation is specifically used when the heat of the reactions is small as the temperature
is an important factor that can influence the selectivity and the conversion of the reactions. The
nonadiabatic operation is employed when there is a large heat of reactions and, as the reactions
stated are very exothermic, it has been decided to operate the reactor by this way. Moreover, the
range recommended of the reactor temperature operation is between 60ºC and 90ºC, so that it
can be assumed that the main reaction is sensitive to the temperature and operating outside this
range may cause a decrease in the yield.
When it comes to nonadiabatic operation, the reactor can be operated in isotherm or in non-
isotherm conditions. In the patent selected is not specified at which temperature the reactants
enter to the reactor, but it is indicated that experimentally it has been cooled to maintain a
temperature in the reactor of 80ºC. It has been decided not to operate in isotherm conditions.
Instead of it, the inlet temperature of the reactants will be 60ºC, the minimum recommended; and
that the reactor will be cooled with an external heat exchanger so that the temperature does not
exceed the 80ºC. By this way, the patent requirements are fulfilled, and it is not withdrawn as
much heat as it would be if the inlet temperature were higher.
6.1.4. Patent requirements

The raw materials stream that enters the reactor accomplish the proportions of 30.9 kilograms
of methacrolein per each 69.1 kilograms of methanol. This stream also conveys the sodium
hydroxide fed in the mixing tank, water as an impurity and the gas phase. The proportion of 7
kilograms of oxygen per each 93 kilograms of nitrogen is also maintained; and the flow rate of the
gas phase is adjusted so that it is in excess and to achieve the main requirements stated in the
patent. To overcome the pressure drop, the pressure of the stream inlet to the reactor tubes if 6
bar.
Table 4: Reaction stream that enter / leaves the reactor
Flow rate (kg/h) R P

C4H6O 5015 1514
CH4O 11214 9568
O2 1756 911
N2 20415 20415
C5H8O2 - 5000
H2O 124 1062
C2H4O2 - 22
CO2 - 32
NaOH 113 113
Total flow rate 38637 38637
Table 5: Verification of the patent requirements
Requirements Patent R P
Stationary weight concentration of methacrolein in the reactor ≤15% 13% 4%
Factor F ≤4 1.6 0.5
In the tables above, R refers to the raw materials stream that enters the reactor, P refers to
the stream that leaves the reactor containing the products of the reactions; and the factor F refers
to the quotient between the liquid volume of the reaction mixture in litres and the catalyst mass in
kilograms.
A first approximation of the mass of catalyst, it is calculated with the space-time yield stated
before. The amount of catalyst introduced in the catalyst will be higher as the reactor will be
oversized, but that will not affect to achieve the requirement because the more catalyst is
introduced, the lower the factor F is for the same liquid volume. As the conditions are achieved
both in the entrance and in the exit of the reactor, it can be assumed that are achieved on the
whole reactor.
6.1.5. Heat of the reactions

The heat generated during the reactions has been calculated taking into account whether the
chemical compounds react in liquid or gas phase and the initial and final temperature. The values
of the constant pressure heat capacity were considered constant in the cases where no more
information was found about its variation with temperature. As the reactions are very exothermic,
it is considered that the temperature increases instantaneously to the temperature maximum
desired of 80ºC in the reactor when the reactions take place. The calculations are attached in the
appendix and the results obtained for each reaction are shown in the table below. In case of the
methyl formate, the calculations have been done based on the global reaction.
Table 6: Enthalpy of reaction and heat generated for each global reaction
Reactions Methyl Methyl Carbon

methacrylate formate dioxide
Enthalpy of reaction (kJ/mol) 297.73 460.76 1453.54
Heat generated (kJ/h) 1.41E+07 1.33E+05 4.87E+05
In the table it can be observed that the main reaction generates most of the heat to remove,
but that the secondary reactions also contributes significantly to generate heat despite its low
selectivity. Therefore, the total heat to withdraw per hour is of 1.137.847 kJ/h, as part of the heat
of the reactions is used to heat the chemical compounds to reach the temperature of 80ºC.
6.1.6. Reactor selection

To select the reactor type, it must be taken into consideration that in laboratory scale, the
reactions were carried out in a tubular reactor, which contained the catalyst. Moreover, as said
before, there is a huge amount of heat to withdraw. Therefore, the reactor that has been chosen
is a multi-tubular fixed bed reactor, as it has more surface to exchange the heat generated by the
reactions due to the fact that it is provided with a great number of tubes and also because it is
more compacted.
The patent indicates the possibility to use slurry bubble column, or a slurry stirred tank instead
when the reactor has a large volume, but a fixed bed reactor would be more suitable to withdraw
the heat generated. In addition these slurry reactors have the drawback that the catalyst must be
constantly fed to the reactor and removed from the effluent of it; and in the case of the slurry
stirred tank, the flow regime would not be the same that in a tubular reactor, which is more closer
to a plug flow.
6.1.7. Reactor design

The design of the reactor is done with the aim to maintain the operation conditions when it is
working, specially prioritizing the control of the temperature over the whole reactor.
Firstly, since in laboratory scale the reactions were carried out inside the tubes, the reactor
will operate in the same way, so that the catalyst is going to be placed inside of them. When it
comes to the flow in the tubes, it is decided to be downward, as most of the reactors of this type
operates by this way to avoid the movement of the catalyst. That implies a great amount of
pressure to be provided by the previous pump and compressor to ensure that both the liquid and
gas phase conveys in that direction and to overcome the pressure drop of the multiphasic reactor.
As far as the refrigerant is concerned, water is chosen as the cooling stream, which enters
and leaves the reactor through the shell side. To control the temperature, the cooling stream
generally conveys in parallel or in cross flow in fixed bed reactors. The possibility of conveying
the water stream in opposite direction from the stream inside the tubes is discarded as this
configuration does not provide a properly control of the temperature. That is because, when the
stream that contains the reactants enter inside the tubes and the reactions start, the tubes would
be in contact with the water stream warmed whereas, when the stream is nearly leaving the tubes,
it would be in contact with the water stream at the lowest temperature; causing that the
temperature inside the tubes is not as stable as in other configurations.
In case of parallel flow, this configuration has the advantage regard the cross flow that the
whole reactor is equipped with tubes. On the other hand, in the inlet and outlet zone the flow is
not uniform, so that only in the central region between the distributor plates can the reaction be
carried out. However, the main disadvantage why it is discarded the parallel flow regarding the
stream inside tubes is because the heat transfer is lower than in cross flow, so that it is not properly
to use this configuration when a large amount of heat needs to be removed.
Therefore, it is decided that the fixed bed reactor is going to be provided with disk and
doughnut baffle plates to ensure a transversal flow of the water stream across the tubes. In this
configuration, it must be taken into consideration that the heat withdrawn by the water is lower at
the extremes of the baffle plates zones, as it is there where water flow is not transversal as it
changes the direction. To solve it, the central zone and the ones nearest the shell are generally
not equipped with tubes (Eigenberger, 1992).
Figure 12: Multitubular fixed bed reactor selected (scheme made with Autocad)
6.1.8. Catalyst type, dimensions and voidage

It is stated in the patent selected the procedure followed to prepare the catalyst and that after
being analysed, the composition determined was of 0.9% of golden and 1.1% of nickel oxide (II)
in a support of magnesia and silicon monoxide. By this way, it can be estimated that the density
of the catalyst is of 2843 kg/m3.
In addition, it is commented that the average diameter of the catalyst in a fixed bed reactor
should be over 200 micrometres, with a maximum particle size of 20 millimetres so that there is
enough area of contact between the catalyst and the reactants.
The ratio between the tube and the particle diameter is an important factor to maintain the
proportion of the void volume in the tubes. Experimentally the catalyst employed was in powder
form with an average diameter of 5 nanometres, but the tube diameter is not specified. Therefore,
this parameter cannot be maintained due to the lack of information. Moreover, the catalyst is these
dimensions are not suitable for the circulation of the streams inside the tubes, so it is
agglomerated in pellets.
There is a wide range of pellets shape to use, so the criteria taken into consideration is to
select that one that has a high surface area per volume and that causes a low pressure drop. It
has been graphed and determined a correlation between the voidage and the ratio between the
tube diameter and the pellet equivalent to a sphere diameter (F. Benyahia et. al., 2005) for
different pellet shapes within a range of pellet dimensions. The voidage is defined as the quotient
between the void volume and the inside tube volume. From the different options purposed, the 4-
hole cylindrical pellets have a great surface area compared to other shapes as spheres and solid
cylinders. Moreover, it has the higher range of voidage, between 0.8 and 0.6, which means that
it will cause the lowest pressure drop. For these reasons, this pellet shape is selected.
Figure 13: Pellet shape selected
In the graphs of the article it can be observed that, when the ratio between the diameters
lessens, the voidage increases rapidly; and when the ratio increases, the voidage lessens until it
is practically constant.
The increase of voidage when the ratio is low is known as wall effect. That happens because,
when the catalyst is filled in the tubes, the catalyst is not uniformly distributed in the region closest
to the walls of the tubes, which lead to a higher void space in that zone. If the catalyst equivalent
diameter increases to much, the non-uniformity is extended along the tube diameter, which has
de drawback that causes the formation of preferential channels, reducing considerably the contact
between the reactants and the catalyst and, subsequently, the yield of the reactor.
On the other hand, under a certain value of catalyst equivalent diameter, it is distributed so
that the voidage is minimum and nearly not affected by it, which is not interesting as the pressure
drop is strongly influenced by the voidage.
The reactor was first designed employing the catalyst so that the voidage in the tubes were
of 0.6 to avoid absolutely the wall effect, but not only the pressure drop was much higher than the
operation pressure but also operating in that conditions would be unaffordable as it would require
a great amount of pressure to be provided by the pump and compressor previous the reactor.
The pressure drop is calculated with the Ergun equation. As the stream inside the tubes is a
mixture of gas and liquid phase, the pressure drop is calculated considering the liquid flow and
that the tube section is the volumetric fraction of the liquid multiplied by the tube section.
Instead of it, the voidage in the tubes has been selected an average value of 0.7 so that the
pressure drop is lower and it is not much affected by the wall effect as it would be if it were the
maximum value of 0.8.
The catalyst pellet dimensions are calculated taking into account that the dimensions and
ratios of the pellet are between those used to determine the correlation, the tubes dimensions
indicated afterwards, and that the pellet diameter is calculated by iteration with the pellet volume
equivalent to sphere diameter. The results are shown as follows.
Table 7: Pellet dimensions

dp (mm) 9.71
dh (mm) 2
H (mm) 12.24
Table 8: Verification of the pellet characteristics

4-hole cylinder pellet Range covered Value considered
H / dp 1.14 – 1.26 1.2
dh 2 – 3.5 2
Tube diameter / dp 1.9 – 8.4 2.25
It can be observed the height and the particle diameter are under the 20 millimetres indicated
as the maximum catalyst size. Therefore, due to the fact that it is not specified the dimensions of
the reactor tubes employed in the patent selected to maintain the ratio previously mentioned, it
can be assumed that the wall effect does not affect the contact between the reactants and the
catalyst negatively enough to lessen the yield of methyl methacrylate.
Another important aspect to bear in mind is the life of the catalyst. The catalyst can be
deactivated after being employed during long periods of time due to chemical, mechanical, or
thermal causes. In this project the process has being designed as if the life of the catalyst is
sufficient long that it does not need to be stopped. However, it has taken into consideration that
the heads are removable so that the catalyst can be replaced.
When it comes to introduce the catalyst into the reactor, it must be ensured that it is filled so
that the pressure drop in each tube is approximately the same with a permissible error of 5%.
Otherwise it may be broken pellets on it or a void space higher than expected (Foumeny et. al.,
2001).
6.1.9. Reactor volume

To determine the reactor tubes volume, firstly is calculated the minimum mass of catalyst with
molar flow of methyl methacrylate produced and the space-time yield. Once calculated, the total
the volume is determined with the density of the catalyst and applying the quotient between void
volume and inside volume equal to 0.7. The total volume of the tubes calculated is 17.3 m3 after
increasing it by a 20% due to security reasons.
It has also been determined the volume with the surface area needed to exchange the heat
generated by the reactions to know if more tubes are needed. This surface area is calculated
knowing that, for cooling the heat generated by the reactions, it is needed 9071 kg of water per
hour that enters at 25ºC and leaves the reactor at 55ºC. The total volume was calculated
employing tubes with the dimensions indicated afterwards, which was lower than the ones
calculated using the space-time yield. Therefore, the volume employed is that calculated with the
space-time yield and the surface area of the tubes is enough to exchange the heat.
6.1.10. Reactor tubes

The reactor cylindrical tubes dimensions are selected from the common employed in heat
exchangers. The number of tubes needed are calculated so that the total internal tubes volume
is achieved. As a high volume is required, a great number of tubes are needed, which is frequent
in this type of reactors. As far as the disposition of the tubes is concerned, they will be in square
configuration because, even though the tubes occupy more space in this configuration, it allows
the mechanical cleaning.
Table 9: Reactor tubes

Number of tubes 4669
Outer diameter (mm) 28.65
Inner diameter (mm) 25.40
Tube length (m) 7.32
Pitch number (m) 0.036
6.1.11. Reactor shell

The reactor shell dimensions are calculated with the bundle diameter of the tubes as if it were
a heat exchanger. However, in this case not all the inside shell reactor is equipped with tubes, so
that the empty spaces must be considered.
It has not been found a way to estimate the distance of the empty spaces related to the reactor
dimensions. Otherwise, in the patent US 9,713,800 it is provided an example of a multi-tubular
fixed bed reactor shell and tube dimensions that has been simulated as well as the diameter of
the central hole surrounded by the tubes. Therefore, as the dimensions of the reactor designed
are similar to it by this way, it has decided to leave the same space in the central zone and, and
the half of it in the zone closest to the shell as the water stream flow rate is the half that when it
conveys across the central zone.
Table 10: Reactor shell

Bundle diameter of the tubes (m) 2.64
Hole space in the central zone (m) 0.75
Void space in the closest zone to the shell (m) 0.375
Inner shell diameter (m) 4.89
6.1.12. Reactor baffles

As far as baffles are concerned, when it is employed disk and doughnut baffles plates in heat
exchangers, this equipment is commonly designed so that the space between this type of baffles
is between 20% and 45% of the shell inside diameter.
However, in the heat exchangers there is no large spaces left without tubes as in the multi-
tubular reactor designed, so that the shell diameter would be way lower for the same number of
tubes. If the reactor baffles are designed as indicated in heat exchangers, it would be very few
baffles and the cross flow of the water stream would not be achieved properly. For this reason, it
has been decided that the spacing between the baffles is of the 20% of the bundle diameter of
the tubes without considering the empty space of the central zone of the shell, increasing the
number of baffles inside the shell.
Table 11: Reactor baffles

Baffle spacing (m) 0.53
Number of baffles 13
Disk baffle diameter (m) 3.4
Doughnut baffle inner diameter (m) 0.75
Doughnut baffle outer diameter (m) 4.89
6.1.13. Reactor materials

The reactor is expected to be constructed with stainless steel AISI 316. This material is slightly
more expensive than the stainless steel AISI 304, which is the ones commonly used, but has the
advantage that is more resistant to corrosion, so that it can last longer time in contact with the
corrosive chemical compounds.
6.1.14. Reactor couplings

The reactor couplings not only needed to support the high pressure of the stream in the tube
side but also, as said before, have to allow the removal of both the heads and the tubes so that
the tubes can be replaced and, as said before, that the catalyst can be replaced.
The diameters of the tubes that enters and leaves the reactor from both shell and tube sides
are shown below. The pipe diameter is calculated so that stream that flows in the tubes side is
conveyed at a velocity of 10 m/s and that the water stream is conveyed at a velocity of 1 m/s. The
diameters are standardized to nominal diameters by choosing the first consecutive diameter
larger than the one determined so that it is available in the marked.
Table 12: Reactor couplings

Nominal diameter
Inlet stream to tube side 300
Outlet stream from tube side 400
Inlet stream to shell side 65
Outlet stream from shell side 65
6.2. PUMPS, FAN AND COMPRESSOR

In the plant it is required equipment to impulse the streams along the plant. Pumps are
employed for the flow of liquids, a fan to impulse the recycling stream towards the gas – liquid
separator, and a compressor for the gas stream that enters the reactor.
It has been made a distinction between the fan and the compressors because the oxygen and
nitrogen stream require both an increase of pressure and temperature to achieve the reactor
operation conditions, and the compressors operating in isentropic would accomplish it while
conveys the gas phase to the reactor. Moreover, the compressors are suitable when it is needed
to highly increase the pressure of the flows, more the other two options indicated.
In this project it is considered that the gas stream is compressed at a pressure of 9 atm,
employing two compressors in series to take advantage of the increase of the temperature to
reduce the energy needed in heating the stream, despite the drawback that a lot energy is
consumed as a great flow rate has to be compressed at this high pressure. It is employed two
compressors because otherwise the compression ratio would be very high for only one
compressor. The compressor ratio it is decided to be the same in both compressors with a value
of 3. The pressure to be compressed considered is higher than the pressure in the entrance of
the reactor as there will be a pressure drop in the pipes and in the heat exchangers.
6.3. GAS – LIQUID SEPARATORS

This equipment consists of a vertical vessel that allows the separation of the gas and liquid
phases by the action of gravity and is favoured by the wire mesh pad deentrainer, which causes
the agglomeration of the liquid droplets so that these precipitates more easily due to their own
weight.
As it is of interest that the liquid is well separated from the gas, so that it is not recycled to the
reactor or lost, depending on which one is referred; it is convenient that it is designed with a higher
pressure and a lower temperature than the inlet stream.
As far as the residence time of the liquid is concerned, it has been considered in the design
of these equipment a time of 20 minutes. Moreover, once the minimum diameter was calculated,
it was adjusted so that the gas-liquid separator does not have a very high height.
Table 13: Gas – liquid dimensions

GL.01 GL.02 GL.03
Gas height (m) 1.8 1.4 1.7
Liquid height (m) 2.2 2.2 2.6
Diameter (m) 1.1 2 1.5
6.4. MIXER AND PH ADJUSTMENT TANK

The mixer tank is designed with a blend time of 30 minutes. This decision has been made to
ensured that there is enough time to adjust the pH with the acid or basic stream, whether it is the
case. The impeller selected is a six pitched blade turbine, as it is stated that is effective for both
turbulent and laminar regime and for solid suspensions such as the sodium hydroxide stream.
Table 14: Tank specifications

Liquid volume (m3) 12.3
Liquid height (m) 8.3
Tank diameter (m) 1.4
Impeller diameter (m) 1
Baffle width (m) 0.1
Blade width (m) 0.2
Impeller height above the vessel floor (m) 0.5
Impeller power (kW) 15.7
6.5. STORAGE TANKS

The storage tank volume is calculated so that the raw materials are stored thirty days of the
capacity demanded for the proper operation of the plant. On the other hand, the sulphuric acid
volume considered is the same one as the sodium hydroxide storage tank.
The sulphuric acid and the sodium hydroxide are stored in a cylindric vertical storage tanks
at atmospheric pressure. On the other side, the methyl methacrylate and the methanol have to
be stored following the ASME regulations as are liquid volatile and flammables.
Table 15: Storage tanks volume

Volume m3
Methanol ST 1519
Sodium hydroxide ST 120
Sulphuric acid ST 120
Methyl methacrylate ST 4597
6.6. HEAT EXCHANGERS

As said before, the heat exchangers 4 and 2 operates in the set-up of the plant or when it is
needed to heat or cool the streams to control the process. Therefore, these heat exchangers have
been designed taking into consideration that when the plant starts to operate the heat exchanges
1 and 3 are not working.
Table 16: Heat exchangers design

Configuration Shell side stream / Tube side stream Number Heat
of tubes (kW)
H.E.01 2- 4 Liquid raw materials/ Recycling 70 88.4
H.E.02 2-4 Water steam/ Liquid raw materials 22 88.4
H.E.03 2-4 Gas raw materials/ Methyl methacrylate 44 51.8
H.E.04 2-4 Water steam/ Gas raw materials 40 84.8
H.E.05 2-4 Water steam/ Methyl methacrylate 71 198
H.E.06 1-2 Methyl methacrylate/ Cold water 430 3411
6.7. PIPING
The diameter of each pipe where the fluids flows between the equipment is calculated
considering the velocities of 1 m/s in case of liquids or 10 m/s in case of gas or liquids and gas
streams. The pipes are indicated according to the stream that flows in it in the same way as the
process flow diagram and the results are shown below. As the reactor, all the pipes are made by
stainless steel AISI 316.
Table 17: Stream pipe diameters
Stream number Nominal diameter

1 40
2 32
3 8
4 8
5 90
6 90
7 6
8 300
9 300
10 400
11 400
12 80
13 350
14 250
6.8. INDUSTRIAL SERVICES
The industrial services needed are water at 130 ºC and 3 bars for heating, as well as water
at 25ºC for cooling. In addition, it would be needed the gas stream of oxygen at 7% of
concentration with nitrogen at the same temperature as a raw material for the reactor.
7. CONCLUSIONS
By all means, it can be concluded that the main objective of this project is accomplished, to
meet the demands of 40.000 tonnes of methyl methacrylate per year by designing a process with
a short pathway that has been enhanced to increase its productivity and feasibility in industrial
scale, even if it requires a further purification for commercialise the product.
The process designed, takes advantage of the temperature of operation to avoid to distillate
the outlet reactor stream to recycle the main raw materials, and also uses its high heat after the
reaction for heating the raw materials, so that the cooling services lessens. Moreover, the reactor
designed is more suitable to exchange the heat of the reactions, and its configuration eases the
control of the temperature. The control of the temperature is an important factor as the process is
temperature-sensitivity so that a poor control of this parameter could lead to a decrease of the
yield amongst other drawbacks, such as an unexpected increase of volume due to the
vaporization of fluid inside it.
However, this process is not very suitable to follow the first part of the direct oxidative
esterification process designed as the methacrolein obtained by it is in a great excess of methanol,
which implies that it would not achieve the requirement of operating under a proportion of liquid
volume lower than the ones required.
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ACRONYMS
O2 = Oxigen
N2 = Nitrogen
H2O = Water
CH4O = Methanol
C2H4O2 = Methyl formate
NaOH = Sodium hydroxide
ST = Storage tank
P.0X = Pump
C.0X = Compressor
GL.0X = Gas-liquid separator
H.E.0X = Heat exchanger
R.0X = Reactor
T= temperature
Cpº= heat capacity
Q = heat
w = mass flow
Hº= Standard enthalpy
Vr = reactor volume
ε= void volume / volume of the reactor
εm = mean voidage
U= Overall heat transfer coefficient
A = Area of exchange
∆Tml = Mean logarithmic temperature difference

Amin = minimum area
n_tubes = number of tubes
Dt = diameter of the tubes
L = length of the tubes
Atubes = surface area of the tubes
Npitch = number of pitch
de = external diameter of the tubes
Dbundle = bundle diameter
Dishell = shell diameter
Dh = hole diameter
Dsurroundings = surroundings distance inside the reactor without tubes
eshell = thickness of the shell
Doshell = outer shell diameter
Bspacing = baffle spacing
DBdisk = diameter of the disk baffle
dpe = particle diameter equivalent to spherical shape
H = particle height
Vp = particle volume
Sp = surface of the pellet
Ф = sphericity
µ = viscosity
vs = velocity inside the tubes
ρ = density
Vtank = Tank volume
DT = Tank diameter
B = Baffle width
Da = Impeller diameter
W = Width of blade
HL = Height of liquid
Za = Height of impeller above the vessel floor
NRe = Reynolds number
N = rotational speed
P = Power
Np = Power number
K = separation constant
ρl = liquid density
ρg = gas density
vgas = maximum gas velocity
dmin = minimum diameter
qg = volumetric flow rate of the gas
Fg = fraction of cross section available for the gas flow
Doutgas = diameter of the nozzle where flows the outlet gas stream
Doutliquid = diameter of the nozzle where flows the outlet liquid stream
Lliquid = height of liquid in the gas liquid separator
Lgas = height of gas in the gas liquid separator
APPENDICES
APPENDIX 1: MASS BALANCE
a) Mass Balance on the Reactor:
- Methacrolein (MAL) consumption for achieve the production demand of methyl

methacrylate (MMA):
40.000.000 kg MMA 1 kmol MMA 1 kmol MAL 100 kmol MAL total 70.09 kg MAL
* * * *
8000 h 100.121 kg MMA 1 kmol MMA 69.8 kmol MAL reacted 1kmol MAL
kg MAL
= 5014.7
h
- Methanol consumption 69.1% in weight regard methacrolein:
kg MAL 69.1 kg CH3OH 𝑘𝑔 𝐶𝐻3𝑂𝐻

5014.7 * = 11214.1
h 30.9 kg MAL ℎ
- Sodium hydroxide inlet and outlet of the reactor as it is 1% in weight regard methanol:
kg CH3OH 1 kg NaOH kg NaOH

11214.1 * =113.3
h 99 kg CH3OH h
- Mass flow rate water inlet to reactor 0.1% regard methanol and 50% regard NaOH:
kg CH3OH 0,1 kg H2O kg NaOH kg H2O kg H2O

11214.1 * +113.3 * =124.5
h 99.9 kg CH3OH h kg NaOH h
- O2 stream inlet to reactor esteemed: 1756.1 kg / h. This flow rate will later be checked if
it accomplishes with the restrictions of the patent.
- N2 inert 93% volume regard O2 that enters and leaves the reactor as it is an inert:
kg O2 1 kmol O2 93 kmol N2 1 kmol N2 kg N2

1756.1 * * ∗ =20414.6
h 32 kg O2 7 kmol O2 28 kg N2 h
- Mass flow rate of methacrolein leaving the reactor as its conversion is 69.8%:
kg MAL kg MAL
5014.7 ∗ (1 − 0,698) = 1514.4
h h
- Mass flow rate of methanol leaving the reactor:
40.000.000 kg MMA 1 kmol MMA 1 kmol CH3OH 100 kmol CH3OH 32,04 kg CH3OH
* * * *
8000 h 100,121 kg MMA 1 kmol MMA 97,2kmol CH3OH 1kmol CH3OH
kg CH3OH consumed
= 1646.2
h
kg CH3OH kg CH3OH consumed kg CH3OH

11214.1 − 1646.2 = 9568.0
h h h
- Mass flow rate O2 leaving the reactor:
• O2 consumed for the formation of MMA:
kg CH3OH consumed 1 kmol CH3OH 97.2 kmol CH3OH consumed in the reaction
1646.2 * *
h 32.04 kg CH3OH 100 kmol CH3OH
0.5 kmol O2 32 kg O2 kg O2
∗ * =799.0
1 kmol CH3OH 1 kmol O2 h
• O2 consumed for the formation of methyl formate (MF):

1646.2 * *
1 kmol O2 32 kg O2 kg O2
∗ * =11.5
• O2 consumed for the formation of CO2:
1646.2 * *
3 kmol O2 32 kg O2 kg O2
∗ * =34.5
Therefore, the total O2 consumed is:
kg O2 kg O2 kg O2 kg O2
799 + 34.5 + 11.5 = 845.0
h h h h
And, subsequently, the mas flow of O2 leaving the reactor is:
kg O2 kg O2 kg O2
1756.1 − 845.1 = 911.0
h h h
- The mass flow rate of N2 leaving the remains invariable as it is inert:
kg N2
20414.6
h
- The mass flow rate of MMA leaving the reactor is:
kg MAL 1 kmol MAL 69.8 kmol MAL reacted 1 kmol MMA 100.121 kg MMA
5014.7 ∗ ∗ ∗ ∗
h 70.09 kg MAL 100 kmol MAL total 1 kmol MAL 1 kmol MMA
kg MMA
= 5000.0
h
- The mass flow rate of MF leaving the reactor is:
kg O2 1 kmol O2 1 kmol MF 60.05 kg MF kg MF

11.5 ∗ ∗ ∗ = 21.6
h 32 kg O2 1 kmol O2 1 kmol MF h
- The mass flow rate of CO2 leaving the reactor is:
kg O2 1 kmol O2 2 kmol CO2 44.01 kg CO2 kg MF

34.5 ∗ ∗ ∗ = 31.6
h 32 kg O2 3 kmol O2 1 kmol CO2 h
Once done the mass balance calculations in the reactor it is verified that with the gas flow rate
established the concentration in weight in both the inlet and the outlet streams inside the tubes
is below 15%.
Table 18: Verification of the concentration of methacrolein in weight in the reactor
Inlet Outlet
Methacrolein % weight 13% 4.09%
b) Mass Balance on the gas – liquid separators:

In these equips the different phases are separated: the gas phase leaves by the upper side
whereas the liquid phase leaves by the lower side. The results are as follows:
Table 19: Gas – Liquid Separator 1 mass balance

GL.01
Mass flow rate (kg/h) 10 11 14
Methacrolein 1514 1514 0
Methanol 9568 9568 0
O2 911 911 0
N2 20415 20415 0
Methyl Methacrylate 5000 0 5000

H2O 1062 0 1062
C2H4O2 22 22 0
CO2 32 32 0
Propionaldehyde 0 0 0
NaOH 113 0 113
Total flow rate 38637 32461 6176

GL.02
Methanol 11214 0 11214
O2 0 0 0
N2 0 0 0
H2O 124 0 124
C2H4O2 0 0 0
CO2 0 0 0
NaOH 113 0 113
Total flow rate 16517 51 16467

GL.03
Methanol 9568 0 9568
O2 911 911 0
N2 20415 20415 0
H2O 0 0 0
C2H4O2 22 22 0
CO2 32 32 0
NaOH 0 0 0
Total flow rate 32461 21379 11082
c) Mass Balance on the mixing and pH adjustment tank:

In the tank, the stream 5 leaves it with the combination of all the other streams:
w1 + w2 + w3 + w4 + w12 = w5
Table 23: Mixing and pH adjustment tank mass balance
Mixing and adjustment pH tank
Mass flow rate (kg/h) 1 2 3 4 12 5
Methacrolein 3500 0 0 0 1514 5015
Methanol 0 1646 0 0 9568 11214
O2 0 0 0 0 0 0
N2 0 0 0 0 0 0
Methyl Methacrylate 0 0 0 0 0 0
H2O 0 11 113 0 0 124
C2H4O2 0 0 0 0 0 0
CO2 0 0 0 0 0 0
Propionaldehyde 51 0 0 0 0 51
NaOH 0 0 113 0 0 113
Total flow rate 3551 1657 227 0 11082 16517
APPENDIX 2: ENERGY BALANCE
a) Energy Balance on the Reactor:

To do the energy balances, it has been found in some cases the correlation of the enthalpy
and the heat capacity with the temperature according to the National Institute of Standards and
Technology (NIST):
HºT – Hº298,15 = A*T + B*T2/2 + C*T3/3 + D*T4/4 – E/T + F – H
Cpº = A + B*T + C*T2 + D*T3 + E/T2
Where:
- T= temperature (K) / 1000
- Cpº= heat capacity (J/mol*K)
- Hº= Standard enthalpy (kJ/mol)
Table 24: Coefficients to estimate standard enthalpy and heat capacity according to
NIST
O2 (g) H2O (l) CO2 (g) N2 (g) NaOH (s)
A 31.32234 -203.606 24.99735 28.98641 419.4837
B -20.23531 1523.29 55.18696 1.853978 -1717.754

C 57.86644 -3196.413 -33.69137 -9.647459 2953.573
D -36.50624 2474.455 7.948387 16.63537 -1597.221
E -0.007374 3.855326 -0.136638 0.000117 -6.046884
F -8.903471 -256.5478 -403.6075 -8.671914 -517.8662
G 246.7945 -488.7163 228.2431 226.4168 933.0738
H 0 -285.8304 -393.5224 0 -425.9312
It has been calculated the heat to increase the temperature of each compound as well as the
heat of reactions. The enthalpy of formations are at 25ºC:
∆Hf C4H6O = -138.5 kJ/mol
∆Hf CH3OH = -238.4 kJ/mol
∆Hf C5H8O2 = -388.8 kJ/mol
∆Hf H2O = -285.83 kJ/mol
∆Hf C2H4O2 = -365.9 kJ/mol
- Reaction of formation of MMA:

∆Hrº = -297.73 kJ/mol
Qr = ∆Hrº · w9r1, MAL
kJ kg MAL 1000 mol MAL 69.8 mol MAL reacted
= -297.73 * 5014.7 ∗ ∗
mol h 70.09 kg MAL 100 mol MAL
= -14868509.1 kJ/h
QMAL = w9r1,MAL · cpMAL · ∆T

kJ kg MAL 1000 mol MAL 69.8 mol MAL reacted
= 99.74·10−3 * 5014.7 ∗ ∗ ∗ (342 − 333)𝐾
mol K h 70.09 kg MAL 100 mol MAL
= 44828.8 kJ / h
QO2 = w9r1,O2 · (Hº353 – Hº298.15)O2- (Hº333 – Hº298.15)O2=14809.8 kJ / h
QCH3OH = w9r1,CH3OH · cpCH3OH · ∆T

kJ mol CH3OH
= 79.9·10−3 * 49940 ∗ (337 − 333)𝐾
mol K h
= 18753.8 kJ / h
QMMA = w9r1,MMA · cpMMA · ∆T

kJ mol MMA
= 191.2·10−3 * 49940 ∗ (353 − 298)𝐾
mol K h
= 525164.6 kJ / h
QH2O= w9r1,H2O · (Hº353 – Hº298.15)H2O- (Hº333 – Hº298.15)H2O = 207042.3 kJ/h
Qt = Qr + Σ Q =-14057909 kJ/h
- Reaction of formation of MF:

∆Hrº = -460.76 kJ/mol
Qr = ∆Hrº · w9r2, CH3OH/2
kJ kg CH3OH 1 kmol CH3OH 1.4 kmol CH3OH consumed in reaction
= -460.8 * 1646.2 * *
mol h 32.04 kg CH3OH 2*100 kmol CH3OH
= -165711.0 kJ/h
QCH3OH = (1/2)* w9r2,CH3OH ·( cpCH3OH (l) · ∆T + ∆Hvap+ cpCH3OH (g) · ∆T) + (1/2)* w9r2,CH3OH ·
( cpCH3OH(l) · ∆T)
kg CH3OH 1 kmol CH3OH 1.4 kmol CH3OH consumed in reaction
= (1/2)* 1646.2 * * ∗
h 32.04 kg CH3OH 2*100 kmol CH3OH
kJ kJ kJ
[79.9·10−3 ∗ (338 − 333)𝐾 + * 37.6 + 46.8·10−3 ∗ (353 − 338)𝐾]
mol K mol mol K
+(1/2)* 1646.2 * * ∗
kJ
[79.9·10−3 ∗ (338 − 333)𝐾]
mol K
= 27830.6 kJ / h
QO2 = w9r2,O2 · (Hº353 – Hº298.15)- (Hº333 – Hº298.15)=213.3 kJ / h
QC2H4O2 = w9,C2H4O2 ·( cpC2H4O2(l) · ∆T + ∆Hvap+ cpC2H4O2 (g))=

mol C2H4O2 kJ kJ kJ
= 49939.6 ∗ [64.38·10−3 ∗ (353 − 325)𝐾 + 29 + 44.06·10−3 ]
h mol K mol mol K
= 7642.1 kJ / h
Qt = Qr + Σ Q =-1334411 kJ/h
- Reaction of formation of CO2:

∆Hrº = -1453.42 kJ/mol
Qr = ∆Hrº · w9r3, CH3OH
kJ kg CH3OH 1 kmol CH3OH 1.4 kmol CH3OH consumed in the reaction
= -1453.42 * 1646.2 * *
mol h 32.04 kg CH3OH 100 kmol CH3OH
= -522761.5 kJ/h
QCH3OH =w9r3,CH3OH ·( cpCH3OH (l) · ∆T + ∆Hvap+ cpCH3OH (g))

=1646.2 * * ∗
kJ kJ kJ
[79.9·10−3 ∗ (338 − 333)𝐾 + * 37.6 + 46.8·10−3 ∗ (342 − 338)𝐾]
mol K mol mol K
= 27830.6 kJ / h
QO2 = w9r3,O2 · (Hº353 – Hº298.15)O2- (Hº333 – Hº298.15)O2=639.9 kJ / h
QCO2 = w9r3,CO2 · (Hº353 – Hº298.15)CO2- (Hº333 – Hº298.15)CO2= 1515.7 kJ / h
Qt = Qr + Σ Q =-486811.0 kJ/h
Table 25: Heat of chemical compounds not reacted:

ni (mol/h) ∆Hi(kJ/mol) Q [kJ/h]
Methanol 298625 38.69 11554287
Methacrolein 21607 34.19 738850
O2 28470 1.62 46253
N2 729092 1.60 1168710
H2O 6917 4.15 28675
NaOH 2832 1.23 9528
Therefore, the total heat is Q = 1131479.1 kJ/h
b) Energy balance on the mixer tank:

In the mixer tank it is calculated the temperature of the outlet stream as the recycling stream
enters at a higher level than the other streams. It is accomplished that:
Q2,MAL + Q11,MAL + Q1,CH3OH + Q11,CH3OH + Q1,CH3OH + Q1,H2O + Q4,H2O + Q2,PROPIONALDEHYDE + Q4,NAOH =0
- Heat of methacrolein:
Q2,MAL= w2,MAL · cpMAL · ∆T=
mol C2H4O2 J
49939.6 ∗ 99.7 ∗ (𝑇𝑜𝑢𝑡𝑙𝑒𝑡 − 298)𝐾
h mol K
Q11,MAL= w11,MAL · cpMAL · ∆T=
mol C2H4O2 J
21607.1 ∗ 99.7 ∗ (𝑇𝑜𝑢𝑡𝑙𝑒𝑡 − 336)𝐾
h mol K
- Heat of methanol:
Q1,CH3OH= w1,CH3OH · cpCH3OH · ∆T=
mol CH3OH J
51378.2 ∗ 79.9 ∗ (𝑇𝑜𝑢𝑡𝑙𝑒𝑡 − 298)𝐾
h mol K
Q11,CH3OH= w1,CH3OH · cpCH3OH · ∆T=
mol CH3OH J
9568 ∗ 79.9 ∗ (𝑇𝑜𝑢𝑡𝑙𝑒𝑡 − 298)𝐾
h mol K
- Heat of water:
Q1,H2O= w1,H2O · cpH2O · ∆T=
mol CH3OH J
51378.2 ∗ 79.9 ∗ (𝑇𝑜𝑢𝑡𝑙𝑒𝑡 − 298)𝐾
h mol K
Q4,H2O= w1,H2O· cpH2O · ∆T=
mol CH3OH J
9568 ∗ 79.9 ∗ (𝑇𝑜𝑢𝑡𝑙𝑒𝑡 − 298)𝐾
h mol K
- Heat of propionaldehyde:
Q1,PROPIONALDEHYDE= w1, PROPIONALDEHYDE · (cp PROPIONALDEHYDE · ∆T + ∆Hvap + cp PROPIONALDEHYDE · ∆T)
=
mol CH3OH J J
872.1 ∗ [134.7 ∗ (322 − 298) + 134.7 ∗ (𝑇𝑜𝑢𝑡𝑙𝑒𝑡 − 322)]
h mol K mol K
- Heat of sodium hydroxide:

Q4,NAOH= w4,NAOH · cpNAOH · ∆T=
mol CH3OH J
113.3 ∗ 59.5 ∗ (𝑇𝑜𝑢𝑡𝑙𝑒𝑡 − 298)
h mol K
Resolving the aforementioned equation it is obtained that the temperature of the outlet stream of
the mixing tank is of 324K which is higher than the propionaldehyde boiling point, so that it
switches to gas phase, just as considered in its heat calculation.
c) Energy to exchange in heat and cold zones:

The heat is calculated in the same way than the previous one, apart from the hot stream 2, where
has taken into account that methanol and methacrolein switch to liquid phase:
Table 26: Energy balance of the cold stream 1 (C1):
Flow Flow Cp Cp T
T intlet
Stream 5 rate rate (J/mol K) (J/mol K) outlet Q (J)
(K)
(kg/h) (mol/h) inlet outlet (K)
Methacrolein 5015 71547 100 324 100 333 6.31E+07
Methanol 11214 350004 80 324 80 333 2.47E+08
H2O 124 6917 75 324 75 333 4.75E+06
Propionaldehyde 51 872 135 324 135 333 1.04E+06
NaOH 113 2832 61 324 61 333 1.92E+06
Q
88.39
(kW)
- Cold stream 2 (C2):

The stream is compressed at a pressure at 9 atm in three isoentropic compressor. The final
temperature after being compressed is calculated by:
𝑘−1
𝑃2 𝑘
Tinlet = 25ºC * ( ) = 46.8º𝐶
𝑃1
Where:
- k is equal to 1,4 for diatomic gases.
- P2 = 9 atm
- P1 = 1 atm
As it is decided to employ two compressors: the ratio of compression is calculated as:
1
𝑃2 𝑛
Ratio = ( ) = 3
𝑃1
Where
- n= number of compressors = 2
In case that n = 1, the ratio would be 9 which is very high for a compressor
Table 27: Energy balance of the cold stream 2 (C2):
Flow rate Flow rate Cp (J/mol T intlet Cp (J/mol T outlet

Stream 8 Q (J)
(kg/h) (mol/h) K) inlet (K) K) outlet (K)
N2 20415 729092 29.14 320 29.15 333 2.82E+08

O2 1756 54878 29.50 320 29.59 333 2.28E+07
Total 22171 783970 - - - - 3.05E+08
Q (kW) 84.80
Table 28: Energy balance of the hot stream 1 (H1):

Stream 14 Q (J)
5000 49940 191.20 353 191.20 303 -4.77E+08

MMA
H2O 1062 59014 75.60 353 75.32 303 -2.28E+08
NaOH 113 2832 59.53 353 61.10 303 -7.11E+06
Total 6062 108954 - - - - -7.13E+08
Q (kW) -197.96
Table 29: Energy balance of the hot stream 2 (H2):

Stream 11 Q (J)
Methacrolein 1514 21607 99.7 353 99.7 336 -7.32E+08

Methanol 9568 298625 79.9 353 37.6 336 -1.15E+10
O2 911 28470 29.7 353 29.6 336 -1.55E+07
N2 20415 729092 29.2 353 29.2 336 -3.66E+08
C2H4O2 22 360 64.4 353 64.4 336 -3.94E+05
CO2 32 719 39.5 353 38.8 336 -6.54E+05
Total 32461 1078873 - - - - -1.26E+10
Q (kW) -3499.43
APPENDIX 3: PINCH ANALYSIS

The following are the streams selected for the analysis, which heat needed or to exchange
has been calculated before. In case of the condenser (H2) it has been determined the average of
the product of the heat capacity and the mass flow.
Table 30: Heat and temperatures displaced
Inlet T Outlet T
w·cp Inlet T Outlet T
Stream corrected corrected Q (kW)
(kW/°C) (°C) (°C)
(°C) (°C)
C1 10.0 51 60 61 70 88.39
C2 6.4 47 60 57 70 84.80
H1 4.0 80 30 70 20 -197.96
H2 205.8 80 63 70 53 -3499.43
In the following table, the heat in each interval is calculated considering the total of the w·cp
products of each current passing through the indicated temperature range. There is no pinch point
as it is defined as there is no interval which value of the heat corrected indicated in Q hoard is 0.
Table 31: Heat cascade

Q hoard (kW)
T intervals Streams Q (kW) 0
70 61 C1, C2, H1, H2 1701.7 1702
61 57 C2, H1, H2 894.8 2596
57 53 H1, H2 797.3 3394
53 20 H1 130.7 3524
APPENDIX 4: REACTOR DESIGN
To carry out the reactor design, firstly it has been calculated the density of the catalyst taking
into consideration that the catalyst was prepared with 108 gr of SiO2 and with 51.2 gr of
magnesium nitrate hexahydrate. Considering that there were no loses of material during the
preparation:
1 mol Mg(NO3 )2 ·6H2O 1 mol MgO 40.304g

51.2 g Mg(NO3 )2 · 6 H2O* * *
256.41g Mg(NO3 )2 ·6H2O 1 mol Mg(NO3 )2 ·6H2O 1mol MgO
= 8.05g MgO
As it is stated that an 1.1% is made by nickel oxide (II), 0.9% is made by gold and the 98%
remaining is made by the support of which the proportions can be estimated and 108 gr of SiO2
per each 8.05 gr of MgO. Therefore, the density of the catalyst (ρcat.) is calculated multiplying
the mass fraction per the density of each of its components:
0.912 * 2634 kg/m3 SiO2 + 0.068 * 3580 kg/m3 MgO+ 0.009*19300 kg/m3 Au+ 0.011*6.67
kg/m3 NiO = 2843 kg / m3 =ρcat.
The mass of catalyst (m. cat) required is calculated with the space time residence:
49940 mol MMA kg catalyst

* =12300 kg of catalyst minimum = 𝑚. 𝑐𝑎𝑡
h 4.08 mol MMA
To verify the second condition of the reactor related to the liquid reactor volume and the mass
of catalyst, it has been determined the volumetric flow rate with the densities of the liquids or solid
and, in case of the gases, applying the ideal gas equation:
Table 32: Volumetric flow rate in the reactor

Volumetric flow rate (m3/h)
Reactants Products
Methacrolein 6 81
Methanol 14 1124
O2 174 107
N2 2317 2744
Methyl Methacrylate 0 5
H2O 0.1 1
C2H4O2 0 1
CO2 0 3
NaOH 0.1 0.1
The volume of the reactor is obtained by the following equation, taking into account that it is
increased a 20% for security reasons:
m.cat
Vr. = *1,2=17,3 m3
ρcat.*(1-ε)
Where:
- Vr.= reactor volume
- ε= void volume / volume of the reactor = 0.7
The area of exchange needed is calculated by:
Q = U A ∆Tml
Where:
- U= Overall heat transfer coefficient (W/m2·ºC)
- A= Area of exchange (m3)
- ∆Tml = Mean logarithmic temperature difference (ºC)
From bibliography is found an U for gases between 20 and 40 BTU/(ft2 h ºF) and a U for
organic solvents between 100 and 300 BTU /(ft2 h ºF). Calculating the mean of these values it is
determined a U of 1306 W/m2 K. Therefore, the area needed minimum employing a water stream
with temperatures of 25ºC and 55ºC is:
Amin = 8.1 m3
The reactor tubes selected are from an internal diameter of 1’’ and a length of 24 ft. The
number of tubes is calculated by:
4 Vr.
𝑛𝑡𝑢𝑏𝑒𝑠 = =4669
Π*dt 2 *L
L
Where:
-dt is the inner diameter of the tubes
- L is the length of the tubes
Once calculated the number of tubes, it is verified that the exchange area is equal or higher
than the needed:
Atubes= π ·dt·L·ntubes = 2271 m3 > Amin
The number of pitch (Npitch) is calculated 1.25 the distance of the external diameter:
Npitch = 1.25 · de = 0.036 m

Where:
-de is the external diameter of the tubes with a value of 28.65 mm
The bundle diameter (Dbundle) without considering the central zone without tubes is
calculated by:
ntubes 1
Dbundle=de* ( ) ^ ( ) =2.64 m
Kt N1
Where Kt and N1 are parameters depending on the number of passes and if it is in square
or triangular configuration. In this case the values of Kt and N1 are 0.215 and 2.207 respectively.
Figure 14: Data to determine the bundle diameter
The shell diameter is calculated considering the baffle spacing of 0.750 m in the central zone
without tubes, and 0,375m in the surroundings closest to the shell wall. Therefore, the shell
diameter is calculated by:
Dishell = Dbundle + Dhole + 2·Dsurroundings = 4.89 m
Taking a thickness shell of 14 mm (eshell), the outer shell diameter is:
Doshell +2·eshell = 4.92 m
The baffle spacing (Bspacing) is calculated as the 20% of the bundle diameter:
Bspacing = 0.2 · Dbundle = 2.64 m
The diameter of the disk baffle (DBdisk) is equal to:

DBdisk= Dbundle + Dhole = 3.39 m
On the other hand, the inner diameter of the doughnut baffle it equal to the diameter of the
central hole: 0.750m; and the outer diameter of the doughnut baffle is equal to the inner shell
diameter: 4.92 m.
When it comes to calculate the dimensions of the catalyst pellet type 4-hole cilinder it has
been taken into account the following data:
Figure 15: Mean voidage – diameter ratio in 4-hole pellets
Figure 16: Characteristics of the particles in the experiments

Table 33: Pellets parameters considered

Mean voidage (εm) 0.7
dt / dpe 2.25
H / dp 1.2
d 2
Where:
- dpe = particle diameter equivalent to spherical shape (mm)
- H = particle height (mm)
- dh = hole diameter (mm)
To calculate its dimensions, firstly is calculated the particle diameter equivalent to spherical
shape with the inner diameter of the tubes and the previous ratio dt / dpe. obtaining a value of:
dpe = 11.29 mm
Afterwards, by iteration it is supposed a value of the particle diameter, it is calculated its

height and volume (Vp), and it is verified if the particle diameter equivalent to the spherical
shape is equal to the previous value calculated:
dp = 9.71 mm
H = dp · H / dp = 12.24 mm
Π *H* dp 2 Π*H * dh 2
Vp = -4 * =753.27 mm
4 4
1/3
6* Vp
dpe = ( ) =11.29 mm
Π
To calculate the pressure drop, it is needed the sphericity of the particle:

Π * dp 2 Π* dh 2
Sp =2* ( -4 * ) +Π * dp *H+4* Π * dh *H=804.22 mm2
4 4
Π * dpe 2
ф= =0.5
Sp
Where:
- Sp = surface of the pellet (mm2)
- Ф = sphericity
As in the reactor tubes conveys liquid and gas phase, the pressure drop is calculated c
considering the liquid flow and the volumetric fraction of the liquid multiplicated by section of the
tube as the section of the tube. The Ergum equation is:
150 ∗ µ ∗ 𝑣𝑠 ∗ (1 − 𝜀)2 1.75 ∗ 𝜌 ∗ 𝑣𝑠 2 ∗ (1 − 𝜀)

∆𝑃 = −𝐿 ∗ [ + ]
2 2
Ф ∗ 𝑑𝑝 ∗ 𝜀 3 Ф ∗ 𝑑𝑝 ∗ 𝜀 3
Where:
- µ = viscosity = 4.11E-4 Pa·s
- vs = velocity inside the tubes = 0.325 m/s
- ρ = density = 853.5 kg/m3
Therefore ∆P = 1.78 atm
Finally, the inlet pressure is: Pinlet = Poperation + ∆P = 7.7 atm

APPENDIX 5: EQUIPMENT DESIGN
a) Mixer tank design:

The mixer tank is designed establishing a blend time of 30 min. Therefore, the effective
volume inside the mixing tank considering that it is increased a 20% for security reasons is:
𝑉𝑡𝑎𝑛𝑘 = 𝑞 ∗ 𝑡𝑏 ∗ 1.2 = 12.3 𝑚3
Where:
- q= volumetric flow rate entering the mixer tank = 20.5 m3/h
- tb= blend time
- 1.2= security factor
The dimensions of the impeller and the tank has been calculated maintaining these ratios.
𝐷𝑇
= 12
𝐵
𝐷𝑎
= 5,66
𝑊
𝐻𝐿
=6
𝐷𝑇
𝑍𝐴
= 1/3
𝐷𝑇
𝐷𝑇
=3
𝐷𝑎
Where:
- DT = Tank diameter = 1.4 m
- B = Baffle width = 0.11 m
- Da = Impeller diameter = 1 m
- W = Width of blade = 0.18 m
- HL = Height of liquid = 8.26 m
- Za = Height of impeller above the vessel floor = 0.46
This mixing tank is equipped with 4 baffles and the impeller is a pitched-blade turbine which
has 6 blades. To calculate power consumed in agitation first is determined the Reynolds number:
𝐷𝑎 2 ∗ 𝑁 ∗ ρ
𝑁𝑅𝑒 = = 2.17 · 106
µ
Where N is the rotational speed, it is selected a value of 140 rpm so that it is well mixed.
Therefore:
- N = rotational speed = 140 rpm

- ρ = 804.9 kg / m3
- µ = 5.62E-04 Pa·s
From the following graph it can be determined a power number (Np) of 1.5 for this type of
impeller and Reynolds number:
Figure 16: Graph number of power – number of Reynolds for different impellers
The power consumed in agitation is:
𝑃 = 𝑁𝑃 ∗ ρ ∗ 𝑁 3 ∗ 𝐷𝑎 5 = 15337 𝑊
b) Gas – liquid separators design:
It is done as example the design of the GL.01.
The gas velocity maximum in the gas liquid separator is calculated as:
1
ρl 2
𝑣𝑔𝑎𝑠 = 𝑘 ∗ [ − 1] = 1.5 𝑚/𝑠
ρg
Where:
- k= separation constant, which has a value of 0.35 because it is employed a mesh
deentrainer.
- ρl = liquid density, in this case 942 kg/m3
- ρg= gas density, in this case 8 kg/m3
The minimum diameter is calculated as:
1
4 ∗ 𝑞𝑔 2
𝑑𝑚𝑖𝑛 = [ ] =
𝐹𝑔 ∗ Π ∗ 𝑣𝑔𝑎𝑠
Where:
- qg= volumetric flow rate of the gas, in this case 4060 m3/h
- Fg = fraction of cross section available for the gas flow. As it is a vertical vessel,
Fg=1
The following heights are considered to design this equipment, therefore:

Figure 17: Gas – liquid separator dimensions considered

The diameter of the nozzle where flows the outlet gas stream is:
1
4 ∗ 𝑞𝑔 2
𝐷𝑜𝑢𝑡𝑔𝑎𝑠 = [ ] = 0.38 𝑚
Π*𝑣𝑜𝑢𝑡𝑙𝑒𝑡𝑔
Where voutlet is the velocity at which the gas stream leaves the equipment established as
10 m/s.
The diameter of the nozzle where flows the outlet liquid stream is:
1
4 ∗ 𝑞𝑙 2
𝐷𝑜𝑢𝑡𝑙𝑖𝑞𝑢𝑖𝑑 = [ ] = 0.048 𝑚
Π*𝑣𝑜𝑢𝑡𝑙𝑒𝑡𝑙
Where voutletl is the velocity at which the liquid stream leaves the equipment established as
1 m/s and ql is the liquid flow rate, in this case 6.4 m3/h.
The height of liquid is calculated as:

4 ∗ 𝑞𝑙 ∗ 𝑡𝑟
𝐿𝑙𝑖𝑞𝑢𝑖𝑑 = 2
= 0.048 𝑚
Π*𝑑𝑚𝑖𝑛
Where tr is the residence time of the liquid established as 20 min.
The height of gas is calculated as:
0.0254 𝑚𝑒𝑡𝑟𝑒𝑠
𝐿𝑔𝑎𝑠 = (12 𝑖𝑛𝑐ℎ + 12 𝑖𝑛𝑐ℎ + 18 𝑖𝑛𝑐ℎ + 12 𝑖𝑛𝑐ℎ) ∗ + 𝐷𝑜𝑢𝑡𝑔𝑎𝑠 = 1.75 𝑚
1 𝑖𝑛𝑐ℎ
c) Heat exchangers design:

. It is done the H.E.01 as an example:
The heat is determined after calculating the energy balances and after applying the Pinch
analysis: Q = 88.4 kW
The heat exchanger area is calculated as:

𝑄 = 𝐹 ∗ 𝑈 ∗ 𝐴 ∗ ∆𝑇𝑚𝑙
In the heat exchangers it is applied a correction factor. In the case were a condensation is
carried out it has a value of 1 and it is selected a configuration of 1 - 2. In other cases, it is
calculated for both configurations 1 - 2 and 2 - 4 regard to the number of passes as and it is
selected the one with higher value:
𝑡2 − 𝑡1
𝑃=
𝑇1 − 𝑡1
𝑇1 − 𝑇2
𝑅=
𝑡2 − 𝑡1
Where:
- t1= temperature of the stream that enters in the tube side.

- t2= temperature of the stream that leaves by the tube side.
- T1= temperature of the stream that enters in the shell side.
- T2= temperature of the stream that leaves by the shell side.
𝐹1−2 = 0,97 ; 𝐹2−4 = 0,94
In this case is selected the configuration 2 – 4 according to the previous results. The overall
heat transfer coefficient is estimated from bibliography between 20 and 60 BTU/(ft2 h ºF).
Therefore, it is selected an overall heat transfer coefficient of a value of 227 W/m2·ºC.
The total area calculated by this way is:
𝐴𝑡 = 19.12 𝑚2
The tubes dimensions selected according to the commonly used are:
Table 34: Tube dimensions

External diameter (mm) 28.65
Internal diameter (mm) 25.4
Length (ft) 10
The exchange area of the tubes is calculated as:
𝐴𝑡𝑢𝑏𝑒 =  ∗ 𝑑𝑒 ∗ 𝐿 = 0.27 𝑚2
The bundle diameter is calculated as in the reactor:

ntubes 1
Dbundle=de* ( ) ^ ( ) = 423 𝑚𝑚
Kt N1
The shell diameter is calculated with the following graph:
Figure 18: Bundle diameter and shell diameter relationship
Therefore, in this case:

Dishell = Dbundle + 11mm = 0,434 m
The outer shell diameter is calculated taking into account a thickness of 3.2 mm:
Doshell +2·eshell = 3.63 m
The baffle spacing is assumed the average between 20% and 45% of the shell diameter.
Baffle spacing = 0.5 m

Number of baffles = 21
Tables 35: Heat exchangers specifications

HEAT EXCHANGER H.E.01
Configuration 2–4 Shell side Tube side
Mass flow (kg/h) 16517 32461
Temperature (inlet/outlet)(K) 353 345 324 333
Q (kW) 88.4 U J/(s*m2*K) 227 ∆Tml (K) 20.5
Shell
Shell inner diameter (m) 0.434 Shell outer diameter (m) 0.437
Tubes
External diameter (mm) 28.65 Internal diameter (mm) 25.40
Thickness (mm) 1.63 Length (m) 3.048
Baffles
Number baffles 21 Spacing (m) 0.14 Thickness (mm) 4.8

Mass flow (kg/h) 7644 32461
Q (kW) 88.4 U J/(s*m2*K) 300 ∆Tml (K) 64.3
Shell
Tubes
Baffles

Q (kW) 51.8 U J/(s*m2*K) 200 ∆Tml (K) 22.5
Shell
Tubes
Baffles

Q (kW) 84.8 U J/(s*m2*K) 150 ∆Tml (K) 66.4
Shell
Tubes
Baffles

Q (kW) 198.0 U J/(s*m2*K) 568 ∆Tml (K) 18.2
Shell
Tubes
External diameter (mm) 28.65 Internal diameter (mm) 25,40
Baffles

Mass flow (kg/h) 282789 32461
Q (kW) 3411.0 U J/(s*m2*K) 483 ∆Tml (K) 37,5
Shell
Tubes
Baffles
d) Storage tanks:
The volume is calculated so that it is storage 30 days. The results are shown below:
- Methanol storage tank
Table 36: Methanol ST volume
Mass flow rate Volumetric flow
(kg/h) rate (m3/h)
Methanol 1646 2
Water 166 1.67E-01
Volume (m3) 1519
- Sodium hydroxide storage tank:
Table 37: Sodium hydroxide ST volume

(kg/h) rate (m3/h)
NaOH 113 5.32E-02
Water 113 1.14E-01
Total flow rate 227 1.67E-01
Volume (m3) 120
- Sulphuric acid storage tank is estimated to have the same volume that the previous
one.
- Methyl methacrylate storage tank:

Table 38: Sodium hydroxide ST volume

(kg/h) rate (m3/h)
MMA 5000 5.32
Water 1062 1.07
Total flow rate 6062 6.38
Volume (m3) 4597

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Treball Final de Grau

Design of a Methyl Methacrylate production plant

Alexander Palacios Ganzevles

3. METHYL METHACRYLATE PROCESS SELECTION 12

5. METHYL METHACRYLATE PROCESS DESIGN 21

REFERENCES AND NOTES 57

APPENDIX 1: MASS BALANCE 64

APPENDIX 2: ENERGY BALANCE 70

APPENDIX 3: PINCH ANALYSIS 78

APPENDIX 4: REACTOR DESIGN 79

APPENDIX 5: EQUIPMENT DESIGN 86

Keywords: Methyl methacrylate, manufacturing process, equipment design, patents

Palabras clave: Metacrilato de metilo, proceso de producción, diseño de equipos, patentes.

Nowadays, methyl methacrylate is present in our lives. It is used to produce polymethyl

Table 1: Main properties of methyl methacrylate

1.2.3. Risks and toxicity

1.2.3.2. Health issues

1.2.4. Environmental impact

3. METHYL METHACRYLATE PROCESS SELECTION

3.1. ETHYLENE PROCESSES

3.1.1. BASF’s process

3.2. PROPYLENE PROCESSES

3.2.1. ACH process

3.2.2. Mitsubishi Gas Chemical Company process

3.3. C-4 FRACTION PROCESSES

3.3.1. Direct oxidation process

3.3.2. Direct oxidative esterification process

3.4. PROCESS COMPARISON

4.1. ASAHI PROCESS

4.2. PATENT US0280628

4.3. PATENT US0251301

4.4. PATENT US0206897

4.5. PATENT COMPARISON

5. METHYL METHACRYLATE PROCESS DESIGN

5.2. RAW MATERIALS

5.3. BLOCK DIAGRAM

Figure 1: Process Blog Diagram

5.4. PINCH ANALYSIS

Table 2: Pinch Analysis results

Figure 3: Compound curves displaced

Figure 4: Grand compound curves

Figure 5: Heat exchange network diagram

Figure 6: Process Flow Diagram previous applying the Pinch Analysis

Table 3: Mass Balance

Figure 6: Process Flow Diagram after applying the Pinch Analysis

6.1.1. Chemical reactions

6.1.1.1. Main reaction

Figure 8: Oxidative esterification reaction of methacrolein

6.1.1.2. Secondary reactions

Figure 9: Incomplete combustion of methanol

Figure 10: Carbonylation of methanol

Figure 11: Complete combustion of methanol

6.1.2.1. Conversion and selectivity

6.1.2.2. Space-time yield

6.1.3. Operation mode

6.1.4. Patent requirements

Flow rate (kg/h) R P