Chinese J. Chem. Eng.

, 14(5) 676684 (2006)

Development and Commercial Application of Methyl-ethyl-ketone

Production Technology

LIU Zhenhua()a,b, HUO Wenzhou()b,*, MA Hao()b and QIAO Kai()b

a
Dalian University of Technology, Dalian 116024, China
b
Fushun Research Institute of Petroleum & Petrochemicals, Fushun 113001, China

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

1 INTRODUCTION other hand, the resin direct hydration process is in

Methyl-ethyl-ketone (MEK) is an organic solvent
that is characterized by satisfactory boiling point,
good solubility, volatilization, and stability and is
nontoxic. It is widely used as a solvent in paint, dye,
pharmaceutical, and refining industries. MEK is also
as an important raw material for organic chemical in-
dustries and is used for the production of MEK perox-
ide and oxime, as an intermediate in the perfumery in-
dustry, as an antioxidant, and for catalyst production[1,2].
With its expanding application in various industries,
the producing capacity of MEK has shown an average
annual increase of 5%10% in many countries. Before
2001, there were only two MEK-production sites in
China, both licensed by Deutsche Texaco Manufacture
Technique, and the annual output was only about
20kta 1, which was far from satisfying the demand of
the domestic market and therefore at least 100kta 1
MEK had to be imported. In 2004, the capacity was
increased to 185kta 1, and the output was 110kta 1.
By 2007, it is predicted that the demand for MEK
would be 230240kta 1 in China[3].
Currently, MEK is commercially produced using
the two-step n-butylene technique: hydrating butylene
to produce secondary butyl alcohol (SBA) and then
dehydrogenating the SBA. Based on different cata-
lysts, there were three main processes: vitriol indirect
hydration, resin direct hydration, and motley acid di-
rect hydration.
Because of huge energy consumption; high cost
of investment; serious equipment cauterization; and
complicated treatment procedures for the exhaust gas,
wastewater, and waste residue, the use of vitriol indi-
rect hydration process declined gradually. In the case
of the motley acid hydration process, the investment is
too high and the operating condition is too rigorous;
therefore, this process is not the best choice. On the
general considered a better choice because the in-
vestment is relatively low and the reaction efficiency
is comparatively high.
There are two ways to produce MEK via dehy-
drogenation of butyl alcohol: gas dehydrogenation and
liquid dehydrogenation. Gas dehydrogenation is widely
used in the industry because it involves a simpler proc-
ess flow sheet and the investment is low. The key to
technical development is the improvisation of the cata-
lyst activity, selectivity, and operation cycle[48].
In China, a large amount of n-butylene exists in
liquefied gas and is mostly used as fuel. MEK has to
be imported from other countries. From the point of
view of resource conservation, the C4 resource will
certainly be used for producing MEK from n-butylene
in the near future in China.
After a thorough investigation of the entire tech-
nology of n-butylene direct hydration and dehydroge-
nation, Fushun Research Institute of Petroleum &
Petrochemicals (FRIPP) developed high-performance,
heat-resistant catalysts for the hydration of butylene
and the FDH-type specialty catalyst for the dehydro-
genation of SBA. On the basis of these, the operating
conditions, such as reaction process parameters, dy-
namics, and thermal stability, were optimized. Under
the optimized operating conditions and with the use of
specialty catalysts, the butylene per pass conversion
was more than 8%, the selectivity of SBA was more
than 98%, the conversion of SBA was greater than
85%, and the selectivity of MEK was more than 96%;
all these techniques have been patented.
Compared with the other licensers, FRIPPs
technology is characterized by the following features:
Hydration reaction adopts low LHSV and high
water/butylenes ratio; therefore, less amount of
recycled butylene is required and energy con-

Received 2005-09-10, accepted 2006-04-17.

* To whom correspondence should be addressed. E-mail: huowenzou@yahoo.com.cn
 Development and Commercial Application of MEK Production Technology
sumption is low;
To recycle water, azeotropic distillation col-
umn is used in this process;
The conversion is improved by lowering the
SBA concentration in recycled water through
the SBA-recovery technique;
Pollution is well controlled by lowering the
concentration of organics in the discharged
water through the recycling of water.
2 EXPERIMENTAL
2.1 Test method and process flow
From the flow chart shown in Fig.1, it can be
seen that n-butylene and deionized water were
pumped into the bottom of hydration reactor, where
the hydration reaction took place. The SBA thus pro-
duced was discharged from the top of the reactor into
the phase-separator. The SBA and unconverted hy-
drocarbons were separated from the water to form the
upper layer, which then entered the distillation column,
where unconverted hydrocarbon was separated from
the SBA. The unconverted hydrocarbon was at the top
of the column, whereas the SBA was at the bottom of
the column. The resultant SBA then entered the inter-
mittent distillation column, wherein it was
separatedlight distillates were at the top of the
column, heavy distillates were at the bottom, and the
SBA product was in the middle. The SBA product then
entered into a vaporizer to boil-off and was then intro-
duced from the top of the vaporizer into the dehydro-
genation reactor. The resultant MEK, from the bottom
of the dehydrogenation reactor, was cooled inside a
condenser and then moved into a phase-separator,
wherein the hydrogen was separated at the top and the
MEK product was obtained at the bottom.
The wastewater containing alcohols discharged
from the bottom of the phase-separator entered the
flash tower where it was distilled. The azeotropic SBA
mixture from the top of the flash tower entered the
intermittent distillation column. The water discharged
from the bottom of the flash tower was treated by both
anion exchange column and ion exchange column, and
was recycled[9,10].
Figure 1 Process flow chart of n-butylene hydration and dehydrogenation
1hydration reactor; 2phase-separator; 3distillation column; 4intermittent distillation column; 5ion column;
6anion column; 7flash tower; 8vaporization; 9dehydrogenation reactor; 10condenser; 11phase-separator
677
Figure 1 shows the procedure for the commercial
production of MEK from a 2L pilot plant reactor, the
capacity was 20kta 1, which was scaled up; the
structure and dimension are as follows.
2.1.1 Hydration reactor
Figure 2 shows the diagram of hydration reactor,
which is a cylinder. The feed hydrocarbon was
pumped from the bottom of the hydration reactor, this
in turn moved upward through the column beds, re-
acted with the deionized water, and, finally, the end
product was discharged from the top of the reactor.
The four sections are similar in design: each is
3m high and 11.25m3 of resin catalyst can be loaded;
therefore, the total amount of catalyst loaded is 45m3.
Each section has a catalyst-loading inlet and a
discharge outlet, a sprayer for water-in, and a derivate
pipe. There is a gas distributor for feed gas under each
catalyst bed, which consists of a gas flier trough and a
bubble cap tray, the feed sprays through the slots of
the bubble cap tray. The sprayer for water-in is located
on the catalyst bed. The feed hydrocarbon was
pumped from the bottom of the hydration reactor.
There is a space of 1.1m height above each sec-
tion to allow thermal expansion, and each bed has a
space of 0.8m height for separating the fogs.
The operating conditions of the hydration reactor
were as follows: reaction temperature, 135175;
reaction pressure, 8.0MPa; LHSV, 1.0h 1 1.2h 1;
mass flow rate of water and butane, 2.02.5; and
online time, 8000ha 1.
2.1.2 Dehydrogenation reactor
Reaction pressure: 0.6MPa. Diameter: 1000mm.
The catalyst loaded in the tubes and heat-conduction
oil of 260320 runs in shells. The volume of
catalyst in each reactor was 700L. There were two
reactors and the structure is as given below. Tubes are
arranged in rows: 25mm2.5mm, the length is
3000mm, total number of tubes is 740, which were
arranged as a normal triangle, and the space between
each tubes is 32mm.
The operating conditions of the dehydrogenation
reactor are: Reaction pressure in inlet, 0.2MPa; re-
action temperature, 250280; LHSV of SBA,
Chinese J. Ch. E. 14(5) 676 (2006)
678 Chinese J. Ch. E. (Vol. 14, No.5)

2.2.2 SBA dehydrogenation

The reaction equation is:
CH3CHOHCH2CH3 CH3COCH2CH3+H2 +Q
Q=51kJmol 1.

The reaction equilibrium constant Kp is:

2.790
lg K p = + 1.510lg T + 1.865
T
The by-reactions are:
2CH3CHOHCH2CH3
CH3CH2CH(CH3)O(CH3)CHCH2CH3H2O
2CH3COCH2CH3H2
CH3CH2C(CH3)CHCOCH2CH3H2O
The process is an endothermic reaction, with the
Figure 2 Diagram of a hydration reactor
number of molecules increasing. From the thermody-
namic point of view, low temperature and high pres-
4.0h 1; the scheduled online time of catalyst, 1 year;

sure will benefit the reaction.
and the period for catalyst regeneration, 68 weeks.
2.3 Feed
2.2 Reaction routes The composition of butylene feed is listed in
2.2.1 n-butylene hydration reaction Table 1.
The general reaction equation of butylene hydra-
tion is: 2.4 Catalyst preparation
n-C4H8+H2O CH3CH(OH)CH2CH3+Q 2.4.1 Specialty resin catalyst of high temperature
This is an exothermic reaction: resistance for butylenes hydration[11]
for n- butylene[1], Q=43kJmol 1

(1) Polymerization reaction
[2]
Q=38.6kJmol 1

for cis-butylene , A total of 64% (by mass) styrene and 7.5% (by
for trans-butylene[3], Q=36.5kJmol 1. mass) divinylbenzene were mixed together, and then

The main by-reactions are:
C4H9OH+n-C4H8
CH3CH2(CH3)CHOCH(CH3)CH2CH3+H2O
2C4H9OH CH3CH2(CH3)CHOCH(CH3)CH2CH3+H2O
(SBE)
The reaction mechanism of ion exchange resin cata-
lyst with strong acid is based on the conversion of buty-
lenes in the presence of H+ to the same carbonium ions:
Through the above-mentioned reversible reac-
tions, the carbonium ion can be reverted to any kind of
butylenes or to SBA alternatively:
27.5% (by mass) 56# paraffin wax and 1% (by mass)
benezoperoxide were added to form the oil phase.
Water phase was obtained using polythene alco-
hol 0.15% (by mass) and methylene blue 0.01% (by
mass), which were then added to deionized water
99.84% (by mass).
The volume ratio of water phase to oil phase was
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-
zation was completed after the polymer resin was pu-
rified by ethanol for 15h, washed, and dried.
(3) Bromination
The polymer resin was initially swelled using

Table 1 The composition of butylene feed (%, by mass)

October, 2006
Propane Propylene n-Butane cis-Butylene-2 trans-Butylene-2 n-Butylene-1 iso-Butylene
0.09 0.22 19.85 31.76 46.54 0.67 0.40
 Development and Commercial Application of MEK Production Technology 679

dichloroethane, and then ferric chloride 1% was added catalyst.

with stirring, with the temperature maintained below
20;subsequently, bromine was slowly added and the
temperature was reduced to 0, After stirring for 10h,
the bromination was completed, after which the poly-
mer resin was filtered, washed, and dried.
(4) Sulfonation reaction
The polymer resin was swelled using dichloro-
ethane. Oleum (50%) was then added slowly with stir-
ring, with the temperature maintained below 30.
Stirring was then continued for 12h at 50. The bro-
minated and strongly acidic cation exchange resin was
obtained after washing sequentially with NaCl solu-
tion, hydrochloric acid, deionized water until the resin
water was neutral.
(5) Active group stabilization
The special high-temperature catalyst for butane
hydration (DNW) was obtained by treating the sulfo-
nic resin that was placed in an autoclave with deion-
ized water that was about 1 time that of the polymer
resin. The resin was heated to 150200 at 1MPa
for 15d and washed using deionized water.
Using the above-mentioned process, for every
batch in the commercial run, 5m3 of DNW speciality
resin high-temperature catalyst could be obtained, and
the total amount of DNW catalyst needed for butane
hydration was 45m3.
The characteristics of the DNW specialty catalyst
are listed in Table 2.
Compared with the traditional methods, the spe-
cialty catalysts that were prepared using the special
method mentioned above had the following excellent
characteristics: (1) high purity; (2) high stability; (3)
after the purification, the pore volume and specific
surface area were increased considerably. So the pore
size would centralize and distribute evenly; the life of
(1) Thermal stability
In a glass tube, whose inner diameter was 10mm,
3ml of catalyst and 6ml of water were added; the glass
tube was sealed and placed in a high-pressure kettle.
At a temperature of 200, the samples were collected
every 8h. Then the exchange capacity of the resin
catalyst and the loss of sulfonic acid group were
measured according to HG2-885-76. The result is
shown in Fig.3.
Figure 3 Static state satuation between the special catalyst
and reference
B-24; DNW catalyst
It can be seen from Fig.3 that the fraction of loss
of sulfo radical was lower than that of the overseas
reference resin catalyst over 64h, which was tested at
200.
(2) Hydration activity
The reaction conditions were as follows: tem-
perature, 150; pressure, 6.0MPa; water/butylene
molar ratio, 1.0; LHSV, 1.5h 1. The result for 120h is
shown in Fig.4.
From Fig.4 it was observed that for 120 h of con-
tinuous running, the average conversion of DNW spe-
cialty resin catalyst was 5.42%, about 5.1% higher
than that of the reference commercial catalyst.

Table 2 The characteristics of hydration catalysts

Item DNW B-24
appearance brown particle bottle-green particle
type strong acid strong acid
+
ion status H type H+ type
water content, % 50.00 57.00
particle size, mm 0.401.20 0.401.20
1
wet specific volume, mlg 0.90 0.95
exchange capacity, molL1 1.30 1.09
2 1
specific surface area, m g 10.0020.00 0.31
The catalyst was produced by Rohm & Hass in the USA.
catalysts was considerably extended, and the loss of
sulfo radicals was decreased.
2.4.2 Comparison of specialty catalyst and overseas
commercial catalyst
To indicate the predominant capability of the
specialty catalyst, the catalytic activity of the DNW
specialty catalyst was compared with that of the B-24
Chinese J. Ch. E. 14(5) 676 (2006)
680 Chinese J. Ch. E. (Vol. 14, No.5)
Figure 4 Reference catalyst and specialty catalyst of high
temperature resistance for hydration reactions
B-24; specialty catalyst for high temperature
2.4.3 Specialty FDH SBA dehydrogenation cata-
lyst[1214]
(1) Preparation of matrix catalyst
Aluminum nitrate (220kg) and zinc nitrate (254kg)
with copper nitrate (338kg) as solution were mixed in
3m3 of deionized water. Sodium carbonate (498kg) and
deionized water (3m3) were mixed as precipitator.
A little deionized water was added into a 10m3
reaction tank to submerge the stirrer and heated to
85, the water solution and precipitator were sepa-
rately heated to 85 and then added to the tank in
parallel-flow, slowly with strong stirring for about
1.5h; the temperature was kept at 85 and pH was
adjusted to 7.08.0 by controlling relative flow-rate
of water solution and precipitator and then sodium
hydroxide solution was added to adjust the pH to 9.5.
The precipitate was washed using deionized water
after aging for 0.5h, it was then dried until the water
content was reduced to 0.5%, uniformly mixed with
25kg graphite, and then it was made into
5mm5mm pellets and calcined at 380 for 6h;
305kg of matrix catalyst was thus obtained and it
contained 46.0% (by mass) copper oxide, 18.5% (by
mass) alumina oxide, and 35.5% (by mass) zinc oxide.
(2) Alkali metals loading
A total of 150kg of the matrix catalyst was added
into a 500L vitreous enamel tank, which had a wa-
ter-cooling system, 300L of niter (1.5molL1) was
Table 3 Characteristics of FDH dehydrogenation catalyst
Item
appearance
particle size, mm
component
pore volume, mlg1
2 1
specific surface area, m g
1
bulk density, gml
average pore diameter, nm
radial crashing strength, MPa
D01 was produced by Deraito in Japan.
Table 4 Comparison of reactivity of different catalysts
Catalyst Conversion of alcohol,%
FDH 81.90
D01 76.80
October, 2006
added and heated for 3h with liquid cycling, then dried,
and calcinated at 360 for 6h. FDH catalyst for SBA
dehydrogenation was thus obtained, which contained
45.4% copper oxide, 18.3% alumina, 35.1% zinc ox-
ide, and 1.2% kalium oxide.
Before being used, catalyst should be activated
by nitrogen/hydrogen mixed gas or SBA under tem-
perature of 150200.
FDH catalyst prepared for SBA dehydrogenation
has advantages, such as high strength, good selectivity,
long running time, low cost, and simple preparation.
The characteristics of the catalyst are listed in Table 3.
2.4.4 Comparison of the specialty FDH dehydroge-
nation catalyst and other catalysts
To show the better capability of the FDH catalyst,
author compared the results of specialty FDH catalyst
on the 200ml secondary butanol test equipment in
miniature with those of the D01 catalyst, which was
produced by JGC in Japan, under the following condi-
tions: temperature, 260; pressure, 0.2MPa; LHSV,
0.34h 1. The results are listed in Table 4. From Table
4 it can be found that of all the catalysts used world-
wide, the FDH catalyst showed maximum reactivity.
3 RESULTS AND DISCUSSION
3.1 Optimization of the n-butylene hydration proc-
ess parameters
3.1.1 Influence of reaction temperature on conver-
sion
Under the conditions of 8.0MPa pressure, 0.34h 1
LHSV, and water/butylene molar ratio of 10, the in-
fluence of reaction temperature on conversion was
investigated in the commercial unit. The results are
shown in Fig.5.
From Fig.5 it can be seen that reaction tempera-
ture had a considerable influence on the conversion.
The higher the temperature, the greater the speed
of reaction until 150. Under the above-mentioned
FDH D01
pellets pellets
55 66
CuO-ZnO-Al2O3 CuO-ZnO
0.150.20 0.12
58.00 36.2 (average)
1.48 1.75
12.00 13.60
14.00 10.00 (average)
Selectivity of MEK, % Selectivity of C8 ketone, %
97.40 2.50
96.80 2.70
 Development and Commercial Application of MEK Production Technology
reaction condition, the concentration of SBA in water
solution is close to the equilibrium concentration; if
the temperature is increased, the by-reaction occurs
easily. So, normally, the reaction temperature cannot
exceed 150.
Figure 5 Curve of temperature to conversion
3.1.2 Influence of reaction pressure on conversion
Under the condition of butylene concentration of
88%, the influence of reaction pressure on conversion
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.
3.1.3 Influence of feed butylene concentration on
conversion
Under the conditions of 8.0MPa pressure, 150
temperature, 0.34h 1 LHSV, and 10 water/butylene
molar ratio, the influence of feed butylene concentra-
tion on conversion was investigated. The results are
shown in Fig.6.
Figure 6 Curve of concentration versus conversion
Table 5 Influence of reaction pressure on conversion
Pressure, Temperature,
Water/butylene mol ratio
MPa
4.00 150 10
6.00 150 10
8.00 150 10
681
From Fig.6, it was observed that the conversion
of butylenes was linear with the feed butylenes con-
centration. The higher the butylenes concentration in
feed, the larger the driving force necessary to drive
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.
3.1.4 Influence of LHSV on conversion
When pressure was 8.0MPa, temperature was
150, and the concentration of butylenes was 88%, the
influence of the water/butylene molar ratio on conver-
sion was investigated. The results are shown in Fig.7.
Figure 7 Influence of water/butylenes on conversion
LHSV 0.2; LHSV 0.34; LHSV 0.5; LHSV 1.0
The influence of LHSV on conversion was inves-
tigated under the following conditions: pressure,
8.0MPa; temperature, 150; and water/butylene mo-
lar ratio, 1.5. The results are shown in Fig.8.
Figure 8 Influence of LHSV on conversion
concentration of butylenc: 99%; 77%
Volume velocity of nC4, Average conversion of butylenes,
h 1
% (mol)
0.34 9.80
0.34 10.10
0.34 10.40
Chinese J. Ch. E. 14(5) 676 (2006)
682 Chinese J. Ch. E. (Vol. 14, No.5)
From Figs.7, 8 it can be observed that wa-
ter/butane molar ratio and LHSV had considerable
influence on conversion and that the conversion of a
related curve became higher as the molar ratio of wa-
ter/butane increased. So, with a fixed water/butanes
molar ratio (or fixed total water amount), total conver-
sion improvement depended on stepping seed.
3.2 Optimization of operating parameters for
SBA dehydrogenation
3.2.1 Influence of temperature
Under normal pressure, LHSV of 4.0h 1 for SBA,
and temperature of 230290, the influence of tem-
perature on SBA conversion and MEK selectivity was
tested with FDH catalyst. The results are shown in Fig.9.
Figure 9 Influence of reaction temperature on conversion
selectivity of MEK; conversion of SBA;
selectivity of C8 ketone
From Fig.9 it can be observed that there was an
obvious increase in the conversion of SBA as the re-
action temperature increased. The conversion of SBA
was above 80% while the temperature was over 250,
and the selectivity of MEK slightly increased, all more
than 95%, and the selectivity of C8 ketone declined.
The by-reaction of SBA dehydration increased when
the reaction temperature continued to rise.
From Fig.10 it can be observed that SBA could
dehydrate and crack easily when the reaction tem-
perature rose, and carbon deposited on catalyst be-
came more concentrated. So, lower reaction tempera-
ture was good for the long-period catalyst operation
and for maintaining adequate SBA conversion.
Figure 10 Variety of butylenes and water to reaction
temperature
Table 6 Influence of reaction pressure on conversion
1
Temperature, LHSV, h Pressure, MPa Conversion of SBA, %
260 4.00 0.10
260 4.00 0.20
260 4.00 0.50
October, 2006
3.2.2 Influence of pressure
The overall reaction is a gas phase reaction in-
creased with the number of molecules, so while the
reaction pressure increased, the conversion of SBA
decreased. The equilibrium conversion of SBA dehy-
drogenation could be expressed as given below:
1
K p 2
X =
P + Kp
2790
lg K p = + 1.510lg T + 1.865
T
where: X, conversion of SBA; P, reaction pressure,
MPa; Kp, equilibrium constant of SBA dehydrogena-
tion, MPa; T, reaction temperature, K.
The relationship of reaction pressure and equilib-
rium conversion is shown in Fig.11.
Figure 11 Relation of equilibrium conversion and
pressure
230; 260
Under the condition of temperature of 260 , the
results of different reaction pressure are listed in Table 6.
From Table 6 it can be observed that the conver-
sion of SBA and the selectivity of MEK decreased
with increase in pressure because of the increasing
rate of the MEK condensation reaction. But for the
pressure drop and industrial equipment controlling,
actual pressure must be about 0.2MPa. Under this
pressure, the conversion of SBA could reach more
than 80% under conditions of temperature of 260
and LHSV of 4.0h 1.
3.2.3 Influence of LHSV
Under normal pressure and temperature of 260,
the influence of LHSV on the conversion of FDH cata-
lysts was investigated. The results are shown in Fig.12.
Figure 12 indicates that the conversion of SBA
decreased with the increase of LHSV, whereas the
MEK selectivity increased. Because the MEK con-
densation reaction slowed down with the decrease in
residence time, the quantity of byproduct C8 ketone
was reduced. If the LHSV was too high, the conver-
sion of SBA was reduced and the circulation of SBA
Selectivity of MEK, % Selectivity of C8 ketone, %
85.33 97.65 2.41
81.81 96.25 3.24
65.34 93.23 6.22
 Development and Commercial Application of MEK Production Technology 683

Table 7 The commercial operating conditions of MEK unit

Item FRIPP Germany technique
hydration reaction
n-butylene concentration, % (by mass) 97.0 97.0
temperature, 135175 160
pressure, MPa 6.0 6.0
LHSV, h1 1.01.5 1.5
water/butylenes ratio 1.01.5 1.0
recycle ratio 10.3 14.0
single pass conversion of butylenes, % 8.011.0 6.0
SBA selectivity, % 98 98
n-butylene conversion, % 90.0 80.0
catalyst volume, m3 23.0 22.0
catalyst life, h 9000 8000
dehydrogenation reaction
temperature, 230260 260
pressure, MPa 0.1 0.2
LHSV, h1 4.0 4.0
SBA conversion, % 96.7 >80.0
MEK selectivity, % 96.6 >95.0
catalyst life, h >3500 10081344
The data was gained in Chinese industry by using technology from Germany.

prolonged. At the same time, the low recycle ratio of

n-butylene resulted in the decreasing of recycling
amount of n-butylene. And the operation cycle of the
dehydrogenation catalyst was prolonged.

Figure 12 Influence of LHSV on conversion
selectivity of MEK; conversion of SBA
increased, so the energy consumption increased. In
general, the conversion of SBA was greater than 80%.
4 CONCLUSIONS
(1) Based on the laboratory and pilot plant stud-
ies in FRIPP, the whole set of production technology
for n-butylene hydration and MEK production by de-
hydrogenation was successfully commercialized. The
two specialty catalysts were both commercialized and
successfully used in the commercial MEK unit.
(2) On the basis of FRIPP technology, a 20kta 1

Under the temperature of 260, the appropriate
LHSV of SBA was around 4.0 h 1.
3.3 Commercial MEK technology
The MEK production technology via n-butylene
hydration/SBA dehydrogenation was commercialized
in a 20kta 1 unit. The specialty resin catalyst of high
temperature-resistance for butylenes hydration and the
specialty FDH SBA dehydrogenation catalyst have
been developed and used in this unit. The unit was
started-up only by one trial, the conversion and selec-
tivity all met the design targets, and MEK product
complied with the ASTM standard. The commercial
results and reference technique data are shown in Ta-
ble 7.
Compared the data listed above, it can be found
that, using the technology developed FRIPP, though
the volume of catalyst is slightly increased, the initial
temperature of reaction was lower than before, the
conversion was enhanced and the life of catalyst was
MEK production unit was built and it operated well
after first starting-up, and the MEK product met the
ASTM standard.
(3) Compared with those of the same kind of
overseas catalysts, the both activity and selectivity of
the two specialty catalysts were excellent.
(4) The MEK production technology is the intel-
lectual property of FRIPP and it reaches the world
advanced level comparable with the other existing
licensors technology.
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