Journal MEK PDF
Journal MEK PDF
Journal MEK PDF
Abstract A synthetic technology for the production of methyl-ethyl-ketone (MEK) is introduced, which makes
use of butylene catalytic hydration to produce secondary butanol (SBA) and this is followed by dehydrogenation of
SBA. By optimizing the operating conditions of a commercial unit, the running results showed that the recom-
mended process was successful and that the catalysts had high activity, good selectivity, and long lifespan, which
ensured long-term running in commercial units.
Keywords methyl-ethyl-ketone (MEK), secondary butanol, hydration, dehydrogenation, resin catalyst
The main by-reactions are: 27.5% (by mass) 56# paraffin wax and 1% (by mass)
C4H9OH+n-C4H8 benezoperoxide were added to form the oil phase.
CH3CH2(CH3)CHOCH(CH3)CH2CH3+H2O Water phase was obtained using polythene alco-
2C4H9OH CH3CH2(CH3)CHOCH(CH3)CH2CH3+H2O hol 0.15% (by mass) and methylene blue 0.01% (by
(SBE) mass), which were then added to deionized water
The reaction mechanism of ion exchange resin cata- 99.84% (by mass).
lyst with strong acid is based on the conversion of buty- The volume ratio of water phase to oil phase was
lenes in the presence of H+ to the same carbonium ions: 4.51.
The water phase was heated to 60 with stirring,
oil phase was added within 2h, and then the stirring
was adjusted to control the size and equality of oil
drops. Solidification of oil drops occurred at 95
100 in 10h. Then, 245833m polymer resin was
obtained after the oil drops were washed with hot wa-
ter, dried, and sieved.
(2) Physics structure stabilization
The polymer resin was swelled for 3h using di-
chloroethane, and unstable components were removed
using series derivatives. The volume of the solvent
was about 3 times that of the polymer resin and was
maintained at 4.0MPa and 160 for 15h. The stabili-
Through the above-mentioned reversible reac- zation was completed after the polymer resin was pu-
tions, the carbonium ion can be reverted to any kind of rified by ethanol for 15h, washed, and dried.
butylenes or to SBA alternatively: (3) Bromination
The polymer resin was initially swelled using
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Development and Commercial Application of MEK Production Technology 681
reaction condition, the concentration of SBA in water From Fig.6, it was observed that the conversion
solution is close to the equilibrium concentration; if of butylenes was linear with the feed butylenes con-
the temperature is increased, the by-reaction occurs centration. The higher the butylenes concentration in
easily. So, normally, the reaction temperature cannot feed, the larger the driving force necessary to drive
exceed 150. n-butylene from the organic phase to the water phase,
which resulted in high n-butylene concentration on
catalyst surface and made the reactions easier.
Apart from n-, cis-, and trans-butylenes, there
were impurities, such as propane, n-butane, propylene,
and iso-butylenes, in the raw material. The partial
pressure of n-butylenes decreased when the impurities
increased; therefore, the impetus of the reaction was
reduced. Therefore, the conversion of the reaction in-
creased with the increase of the concentration of
n-butylenes.
Figure 5 Curve of temperature to conversion 3.1.4 Influence of LHSV on conversion
When pressure was 8.0MPa, temperature was
3.1.2 Influence of reaction pressure on conversion 150, and the concentration of butylenes was 88%, the
Under the condition of butylene concentration of influence of the water/butylene molar ratio on conver-
88%, the influence of reaction pressure on conversion sion was investigated. The results are shown in Fig.7.
was observed. The results are shown in Table 5.
It was found that the reaction pressure could con-
siderably affect the hydration of butylenes. When
temperature was 150, the saturated vapor pressure
of water, cis-butylene-2, and trans-butylene-2 was
4.918MPa, 3.435MPa, and 3.712MPa, respectively.
The total saturated vapor pressure was about 4.0MPa.
When the pressure reached 5.0MPa, n-butylene ex-
isted under the condition of supercritical pressure. The
effect of increase of pressure on the solubility of
n-butylene seemed negligible. Figure 7 Influence of water/butylenes on conversion
3.1.3 Influence of feed butylene concentration on LHSV 0.2; LHSV 0.34; LHSV 0.5; LHSV 1.0
conversion
Under the conditions of 8.0MPa pressure, 150 The influence of LHSV on conversion was inves-
temperature, 0.34h 1 LHSV, and 10 water/butylene
tigated under the following conditions: pressure,
molar ratio, the influence of feed butylene concentra- 8.0MPa; temperature, 150; and water/butylene mo-
tion on conversion was investigated. The results are lar ratio, 1.5. The results are shown in Fig.8.
shown in Fig.6.
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Development and Commercial Application of MEK Production Technology 683
4 CONCLUSIONS
(1) Based on the laboratory and pilot plant stud-
ies in FRIPP, the whole set of production technology
Figure 12 Influence of LHSV on conversion
for n-butylene hydration and MEK production by de-
selectivity of MEK; conversion of SBA
hydrogenation was successfully commercialized. The
two specialty catalysts were both commercialized and
increased, so the energy consumption increased. In successfully used in the commercial MEK unit.
general, the conversion of SBA was greater than 80%. (2) On the basis of FRIPP technology, a 20kta 1
Under the temperature of 260, the appropriate MEK production unit was built and it operated well
LHSV of SBA was around 4.0 h 1.
after first starting-up, and the MEK product met the
ASTM standard.
3.3 Commercial MEK technology (3) Compared with those of the same kind of
The MEK production technology via n-butylene overseas catalysts, the both activity and selectivity of
hydration/SBA dehydrogenation was commercialized the two specialty catalysts were excellent.
in a 20kta 1 unit. The specialty resin catalyst of high
(4) The MEK production technology is the intel-
temperature-resistance for butylenes hydration and the lectual property of FRIPP and it reaches the world
specialty FDH SBA dehydrogenation catalyst have advanced level comparable with the other existing
been developed and used in this unit. The unit was licensors technology.
started-up only by one trial, the conversion and selec-
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October, 2006