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

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 recommended 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

INTRODUCTION
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 industries and is used for the production of MEK peroxide and oxime, as an intermediate in the perfumery industry, 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 catalysts, there were three main processes: vitriol indirect
hydration, resin direct hydration, and motley acid direct 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 indirect 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

other hand, the resin direct hydration process is in

general considered a better choice because the investment is relatively low and the reaction efficiency
is comparatively high.
There are two ways to produce MEK via dehydrogenation of butyl alcohol: gas dehydrogenation and
liquid dehydrogenation. Gas dehydrogenation is widely
used in the industry because it involves a simpler process flow sheet and the investment is low. The key to
technical development is the improvisation of the catalyst 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 technology of n-butylene direct hydration and dehydrogenation, 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 dehydrogenation of SBA. On the basis of these, the operating
conditions, such as reaction process parameters, dynamics, 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 column 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 produced was discharged from the top of the reactor into
the phase-separator. The SBA and unconverted hydrocarbons 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 intermittent 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 introduced from the top of the vaporizer into the dehydrogenation 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].

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, reacted 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 section 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; reaction temperature, 250280; LHSV of SBA,

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
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Chinese J. Ch. E. (Vol. 14, No.5)

678

2.2.2 SBA dehydrogenation

The reaction equation is:
CH3COCH2CH3+H2 +Q
CH3CHOHCH2CH3

Q=51kJmol 1.
The reaction equilibrium constant Kp is:
lg K p =

Figure 2

Diagram of a hydration reactor

4.0h 1; the scheduled online time of catalyst, 1 year;

and the period for catalyst regeneration, 68 weeks.

2.2 Reaction routes

2.2.1 n-butylene hydration reaction
The general reaction equation of butylene hydration is:
CH3CH(OH)CH2CH3+Q
n-C4H8+H2O
This is an exothermic reaction:

Q=43kJmol 1
for n- butylene[1],

[2]
for cis-butylene ,
Q=38.6kJmol 1

for trans-butylene[3], Q=36.5kJmol 1.

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 catalyst with strong acid is based on the conversion of butylenes in the presence of H+ to the same carbonium ions:

Through the above-mentioned reversible reactions, the carbonium ion can be reverted to any kind of
butylenes or to SBA alternatively:

October, 2006
Propane
0.09

Table 1

2.790
+ 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
number of molecules increasing. From the thermodynamic point of view, low temperature and high pressure will benefit the reaction.
2.3

Feed
The composition of butylene feed is listed in
Table 1.
2.4 Catalyst preparation
2.4.1 Specialty resin catalyst of high temperature
resistance for butylenes hydration[11]
(1) Polymerization reaction
A total of 64% (by mass) styrene and 7.5% (by
mass) divinylbenzene were mixed together, and then
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 alcohol 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 water, dried, and sieved.
(2) Physics structure stabilization
The polymer resin was swelled for 3h using dichloroethane, 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 stabilization was completed after the polymer resin was purified by ethanol for 15h, washed, and dried.
(3) Bromination
The polymer resin was initially swelled using

The composition of butylene feed (%, by mass)

Propylene

n-Butane

cis-Butylene-2

trans-Butylene-2

n-Butylene-1

iso-Butylene

0.22

19.85

31.76

46.54

0.67

0.40

Development and Commercial Application of MEK Production Technology

dichloroethane, and then ferric chloride 1% was added

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 polymer resin was filtered, washed, and dried.
(4) Sulfonation reaction
The polymer resin was swelled using dichloroethane. Oleum (50%) was then added slowly with stirring, with the temperature maintained below 30.
Stirring was then continued for 12h at 50. The brominated and strongly acidic cation exchange resin was
obtained after washing sequentially with NaCl solution, 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 sulfonic resin that was placed in an autoclave with deionized 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 specialty 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
Table 2

catalyst.
(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: temperature, 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 continuous running, the average conversion of DNW specialty resin catalyst was 5.42%, about 5.1% higher
than that of the reference commercial catalyst.

The characteristics of hydration catalysts

DNW

B-24

brown particle

bottle-green particle

strong acid

strong acid

Item
appearance

679

type

H type

H+ type

50.00

57.00

0.401.20

0.401.20

wet specific volume, mlg

0.90

0.95

exchange capacity, molL1

1.30

1.09

10.0020.00

0.31

ion status
water content, %
particle size, mm
1

specific surface area, m g

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
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Chinese J. Ch. E. (Vol. 14, No.5)

680

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 catalyst[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 separately 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 water-cooling system, 300L of niter (1.5molL1) was
Table 3
appearance
particle size, mm
component
pore volume, mlg1
1

specific surface area, m g

bulk density, gml

3 RESULTS AND DISCUSSION

3.1 Optimization of the n-butylene hydration process parameters
3.1.1 Influence of reaction temperature on conversion

Under the conditions of 8.0MPa pressure, 0.34h 1

LHSV, and water/butylene molar ratio of 10, the influence 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 temperature had a considerable influence on the conversion.
The higher the temperature, the greater the speed
of reaction until 150. Under the above-mentioned

Characteristics of FDH dehydrogenation catalyst

Item

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 oxide, and 1.2% kalium oxide.
Before being used, catalyst should be activated
by nitrogen/hydrogen mixed gas or SBA under temperature 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 dehydrogenation 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 conditions: 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 worldwide, the FDH catalyst showed maximum reactivity.

average pore diameter, nm

radial crashing strength, MPa

FDH
pellets
55

D01
pellets
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)

D01 was produced by Deraito in Japan.

Table 4
Catalyst
FDH
D01
October, 2006

Comparison of reactivity of different catalysts

Conversion of alcohol,%
81.90
76.80

Selectivity of MEK, %
97.40
96.80

Selectivity of C8 ketone, %
2.50
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 considerably 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 existed 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 concentration on conversion was investigated. The results are
shown in Fig.6.

Figure 6

Curve of concentration versus conversion

681

From Fig.6, it was observed that the conversion

of butylenes was linear with the feed butylenes concentration. 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 increased 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 conversion 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 investigated under the following conditions: pressure,
8.0MPa; temperature, 150; and water/butylene molar ratio, 1.5. The results are shown in Fig.8.

Figure 8 Influence of LHSV on conversion

concentration of butylenc: 99%; 77%

Table 5
Pressure,
MPa

Temperature,

Influence of reaction pressure on conversion

Volume velocity of nC4,
Water/butylene mol ratio

h 1

Average conversion of butylenes,

% (mol)

4.00

150

10

0.34

9.80

6.00

150

10

0.34

10.10

8.00

150

10

0.34

10.40
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Chinese J. Ch. E. (Vol. 14, No.5)

682

From Figs.7, 8 it can be observed that water/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 water/butane increased. So, with a fixed water/butanes
molar ratio (or fixed total water amount), total conversion 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 temperature 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 reaction 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 temperature rose, and carbon deposited on catalyst became more concentrated. So, lower reaction temperature 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

Temperature,
260
260
260
October, 2006

LHSV, h
4.00
4.00
4.00

3.2.2 Influence of pressure

The overall reaction is a gas phase reaction increased with the number of molecules, so while the
reaction pressure increased, the conversion of SBA
decreased. The equilibrium conversion of SBA dehydrogenation could be expressed as given below:
1

K p 2
X =

P + Kp

2790
+ 1.510lg T + 1.865
lg K p =
T
where: X, conversion of SBA; P, reaction pressure,
MPa; Kp, equilibrium constant of SBA dehydrogenation, MPa; T, reaction temperature, K.
The relationship of reaction pressure and equilibrium 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 conversion 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 catalysts 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 condensation reaction slowed down with the decrease in
residence time, the quantity of byproduct C8 ketone
was reduced. If the LHSV was too high, the conversion of SBA was reduced and the circulation of SBA

Influence of reaction pressure on conversion

Pressure, MPa
0.10
0.20
0.50

Conversion of SBA, %
85.33
81.81
65.34

Selectivity of MEK, %
97.65
96.25
93.23

Selectivity of C8 ketone, %
2.41
3.24
6.22

Development and Commercial Application of MEK Production Technology

Table 7

683

The commercial operating conditions of MEK unit

Item
hydration reaction
n-butylene concentration, % (by mass)
temperature,
pressure, MPa
LHSV, h1
water/butylenes ratio
recycle ratio
single pass conversion of butylenes, %
SBA selectivity, %
n-butylene conversion, %
catalyst volume, m3
catalyst life, h
dehydrogenation reaction
temperature,
pressure, MPa
LHSV, h1
SBA conversion, %
MEK selectivity, %
catalyst life, h

FRIPP

Germany technique

97.0
135175
6.0
1.01.5
1.01.5
10.3
8.011.0
98
90.0
23.0
9000

97.0
160
6.0
1.5
1.0
14.0
6.0
98
80.0
22.0
8000

230260
0.1
4.0
96.7
96.6
>3500

260
0.2
4.0
>80.0
>95.0
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.
4
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%.
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 selectivity all met the design targets, and MEK product
complied with the ASTM standard. The commercial
results and reference technique data are shown in Table 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

CONCLUSIONS
(1) Based on the laboratory and pilot plant studies in FRIPP, the whole set of production technology
for n-butylene hydration and MEK production by dehydrogenation 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

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 intellectual property of FRIPP and it reaches the world
advanced level comparable with the other existing
licensors technology.

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