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TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES

363 P. Casal St., Quiapo, Manila

College of Engineering and Architecture


CHEMICAL ENGINEERING DEPARTMENT

CHE 511
Plant Design

Review of Related Literature


Development of a commercial process to produce Tetrahydrofuran

Submitted By:
Alarcon, Grace Dianne A.
CH52FC1

Submitted To:
Engr. Lina D. Dela Cruz

Date Submitted:
June 28, 2017
Review of Related Literature

Hydrogenation of Maleic Acid to Tetrahydrofuran


Michael Abuschinow, Daniyal Hussain, Kathleen Wu
University of Pennsylvania

Product Description
Tetrahydrofuran is a colorless, water-miscible, flammable liquid with an odor resembling
that of ether. Its IUPAC name is Oxacyclopentane. It is a volatile general purpose organic solvent
and can be used as starting material for various chemical syntheses.
In industry, it is primarily used as a solvent for numerous polymers and resins. It also has
extensive uses in the production of rubber, cellophane, adhesives, magnetic tape and printing
inks. Under strongly acidic conditions, THF polymerizes to form Polytetramethylene Ether
Glycol (PTMEG), which is utilized in the manufacture of various flexible and elastic fibers. THF
is also present in the adhesives used to join plastic pipes for well construction and water
treatment systems, and since THF is a component of food packaging adhesives, it can be an
indirect food additive. It is also frequently used as a solvent in numerous pharmaceutical
synthesis procedures.
THF reacts readily with oxygen to form peroxides, which are unstable and decompose in
stages to produce organic acids. Therefore, to maintain the purity of THF, it must be stored away
from the presence of oxygen. An increase in peroxide concentration can be detected by the
appearance of color in the liquid as well as the formation of peroxide residues on the tank walls

Methods of Production
The internal research and development division recommended a vapor-only reactor
effluent method of producing THF. This chemical reaction process was chosen because it
prevents downstream separation equipment from fouling since only volatile compounds are able
to leave the reactor. The plant uses maleic acid produced in an internally-owned, upstream
facility and hydrogen from pipelines in the Gulf Coast. Maleic acid is hydrogenated in an
aqueous environment within a single back-mix tank reactor to form THF. Intermediates include
succinic acid, gamma-butyrolactone (GBL), and 1,4- butanediol (BDO). Unfortunately, several
side reactions lead to the formation of undesired products including methane, propane, n-butane,
propanol, and n-butanol. Thus, an extensive separation train is required to remove the liquid
intermediates, alkanes, and alcohols, and to ultimately break a water-THF azeotrope. The final
product stream consists of 99.97% pure THF by mass.

Raw Materials
The two raw materials used in this process are hydrogen and maleic acid. Hydrogen is
readily available by pipeline at 68F and 250 psig and costs $0.75/lb. The maleic acid is
produced in an internally-owned plant and is transported via pipeline at a transfer price of
$0.45/lb maleic acid, on an anhydrous basis. It is available at 94F and 5 psig and at a maximum
60% by weight maleic acid in water.
At purities greater than 60%, the maleic acid begins to separate from the solution.

Reaction Train
Maleic acid is hydrogenated to THF via a series of simultaneous reactions in a back-mix
tank reactor. The reactions are a series of hydrogenations in which bonds are broken in the
reacting maleic acid and chemical intermediates. Since hydrogen gas does not readily react with
the compounds, the reactor contains palladium-rhenium (Pd-Re) catalyst coated on carbon
support. The carbon maximizes the available surface area for the reaction to occur and the
palladium and rhenium metals provide active sites for the hydrogen to be adsorbed. Thus,
hydrogen is more readily available to react when intermediates comes in contact with it.
Operating conditions of 2000 psig and 480F were provided by the internal R&D
department as ideal for the reaction. A tank reactor was selected in order to provide maximum
agitation and exposure of the catalyst and hydrogen to the liquid reactants. Agitation is provided
by the hydrogen bubbling from the bottom of the reactor. All reaction occurs in the liquid phase,
but it was found desirable to only take a vapor product off the top of the reactor to keep
downstream separation processes clean. The 8 hydrogenation reactions are highly exothermic,
and the heat of reaction is used to vaporize the THF product and other liquid compounds,
allowing the reactor to operate adiabatically. First, maleic acid (MAC) is nearly completely
converted to succinic acid (SAC), which is then converted into gamma butyrolactone (GBL), a
heavy liquid intermediate. GBL is then simultaneously hydrogenated to either 1,4-butanediol
(BDO), another heavy liquid intermediate, or THF. GBL is also hydrogenated into the
byproducts propane, n-butane, propanol, and n-butanol, with a byproduct split of 0.15 butane and
0.85 butanol and 0.10 propane and 0.90 propanol. Byproduct splits were provided by the internal
R&D department as reasonable splits given the reactor conditions. BDO is further hydrogenated
to THF and forms the same byproducts with the same splits as GBL. THF also undergoes
undesirable hydrogenation at the reactor conditions, forming the same alkane and alcohol

byproducts. The reactions are summarized below as Reactions 0 through 7b.


Production of tetrahydrofuran by dehydration of 1,4-butanediol using Amberlyst-15: Batch
kinetics and batch reactive distillation
Vijay M. Shindea, Ganesh N. Patila, Amit Katariyab, Yogesh S. Mahajana,*
a Chemical Engineering Department, Dr. B. A. Technological University, Lonere, Tal. Mangaon,
Raigad, Maharashtra 402 1032, India b Praj Matrix Innovation Centre, S. No. 402, 403, 1098,
Urwade, Tal. Mulshi, Pune, Maharashtra 412 115, India

Materials and methods of analysis


BD, isopropyl alcohol (IPA), THF and the solvent, 1,4-dioxane (all AR grade) were
obtained from S.D. Fine-Chem Ltd., India. Amberlyst-15 (A-15) was obtained from Rohm and
Haas, France (refer Table 1 for important properties). Catalyst was washed and dried for 24 h at
378 K under vacuum (50 mm Hg) before its use in the reaction. Samples were withdrawn from
the reactor at regular time intervals and analyzed using a gas chromatograph (Chemito- 8610)
equipped with a flame ionization detector (FID). 2.44 m long column (Porapack-Q) was used to
separate the components with isopropyl alcohol (IPA) as the standard. The injector, detector and
the oven temperature were maintained at 523 K each. Water content in samples was analyzed
with a gas chromatograph (NUCON 5765) equipped with thermal conductivity detector. A
packed column (Porapack-Q, length 1.82 m, O.D. 1/8 in., material- SS) was used for separation.
For preparation of the GC samples, a solution of collected samples with known amount of
anhydrous IPA as a standard was prepared. The oven temperature program consisted of 150 C
isothermal for 1 min and ramp at 5 C/min to 240 C. The injector and detector temperature was
maintained at 240 C. Using the standard calibration curves that were prepared for all the
components, the integrated areas were converted to weight percentages for each component
present in the sample which were then converted into moles. All samples were injected twice to
confirm reproducibility. Experimental results thus obtained were within 3% of experimental
error. The total quantity of samples removed represented only a small fraction of the total
reaction mass and hence does not contribute significantly to changes in the volume of reaction
mass. Conversion of BD is calculated according to Eq. (1).
Batch Kinetics
A mechanically agitated, three neck glass reactor of 5 x10 -4 m3 capacity having a four
blade glass baffle was used to carry out all the batch runs. A constant-temperature bath was used
to control the temperature with 1 C. For all the batch experiments, BD in the reactor was 203
gm (2 x10-4m3). The presence of a diluent has been reported to reduce the overall rate and yield
of THF (2 3). Hence, all the experiments were carried out with pure BD except Fig. 1.
Production of THF from 1, 4-butanediol. for those performed to study the effect of solvent where
calculated amounts of the solvents were added to the above mentioned amount of BD. The
catalyst loading employed was over the range 510% (w/w). A range of temperature from 343 K
to 363 K was employed for the batch runs. An ice-cooled condenser was used to ensure minimal
losses as THF is highly volatile and is having a low boiling point 339 K. It is important to note
here that although temperature used in most batch kinetic runs is less than 373 K, the boiling
point of THF and also of the azeotrope (337 K) are still lower than this. Thus, in order to make
sure that the losses were almost absent, ice cooled water was used for condensation. When the
desired temperature was reached, zero time _sample was collected. Catalyst was separately
heated to the desired temperature and it was added to the reaction mass just after drawing the
zero time _sample. The samples were collected from the reaction vessel via a specially
designed sampling tube fitted with filter at the bottom thus ensuring that no catalyst was present
in the samples.
Evaluation of Zeolites in Production of Tetrahydrofuran from 1,4-Butanediol:
Performance Tests and Kinetic Investigations
Mahmoud Aghaziarati, Mohammad Kazemeini,* Mohammad Soltanieh, and Saeed Sahebdelfar
Department of Chemical and Petroleum Engineering, Sharif UniVersity of Technology, Azadi AVenue, P.O. Box
11365-9465, Tehran, Iran

Materials
BDO and 1,4-dioxane with minimum purityof 99% were supplied by Merck Chemicals.
Five different types of zeolites with large, medium, and small pore sizes, namely, Y, Mordenite,
Beta, ZSM-5, and Ferrierite, were studied. The zeolites were obtained from the Zeolyst Company
(United States). The zeolites as received were in Na-form. Alumina and silica were supplied by
Merck Chemicals. To determine the influence of cation, Na-form zeolite samples were ion-
exchanged to NH4 + form using an aqueous solution of NH4NO3. They were subsequently dried
at 373 K for 24 h. H+-form zeolites were prepared by calcination of NH4 +-form samples at a
constant rate of temperature rise (2 K/min) from 373 to 773 K and by keeping the temperature at
773 K for 5 h.

Characterization
After the aforementioned treatments, the zeolites were characterized by standard
methods. For this purpose, Si/Al ratio and surface area of zeolites were measured by MASNMR
spectroscopy and N2 adsorption-desorption methods, respectively. The atomic ratio (Si/Al) of Si
and Al in the zeolite samples was determined by MASNMR. The zeolite samples were hydrated
in a desiccator with saturated aqueous solution of NH4- Cl at room temperature for 24 h to
minimize the line width of Al. The MASNMR spectra were recorded at 53.7 and 70.4 MHz
(referenced to TMS and Al(H2O)6 3+), for Si and Al, respectively, on a pulsed Fourier transform
nuclear magnetic resonance (NMR) spectrometer (JNM-GX270, JEOL), which was equipped
with a CP/MAS unit (NM-GSH27MU JEOL). All NMR spectra combined with magic-angle
spinning (MAS) spectra were recorded with H-decoupling during data acquisition.
Crosspolarization (CP) was not employed, since the protons of zeolite samples are not directly
attached to Si or Al. Each spectrum was recorded with 8 K data points and consisted of 700-1300
accumulated scans. The surface area of the samples was measured by a multipoint N2
adsorption-desorption method at liquid N2 temperature (-196 C) with a Micromeritics TriStar
3000 surface area analyzer. Samples were outgassed under vacuum to remove the physisorbed
water immediately before analysis.
Catalytic Reactions
Catalyst performance tests were carried out in a 500-mL autoclave. This reactor was
equipped with variable speed stirrer, cooling coil, and proportionalintegral- derivative (PID)
controller. Maximum operational temperature and pressure were 350 C and 100 bar,
respectively. The experimental setup is shown in Figure 2. To operate near isothermal conditions
and to minimize catalyst deactivation effects, a known quantity of BDO was dissolved in 1,4-
dioxane as the solvent and the mixture was charged into the reactor along with a predetermined
quantity of catalyst. The reactor was then flushed several times with nitrogen. Reaction was
induced by bringing the reaction mass to the reaction temperature and turning on the agitation.
The reaction was essentially a liquidphase reaction with the solid catalyst suspended uniformly
in the liquid medium in the form of slurry. During reaction, liquid samples were withdrawn from
the reactor and were analyzed for the consumed BDO. The experimental conditions and
parameters and their ranges are given in Table 1.

After determining the optimum catalyst, experiments were designed by Taguchi


method22 to investigate the effects of the key parameters such as temperature, pressure, and
substrate concentration. The resulting test conditions employed in this work are given in Table 2.

Analytical Methods
The analysis of the liquid product samples was carried out using a gas chromatograph
(Chrompack, CP 9001) equipped with Porapak Q column and FID detector, with helium as the
carrier gas. Injector and detector temperatures were 270 and 300 C, respectively. It was ensured
that the total quantity of samples removed from the reactor represented only a small fraction of
the total reaction mass and hence does not contribute significantly to changes in the volume of
this mass. The material balance was found satisfactory. The error in this analysis was in the range
of 3%-5%.