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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 general considered a better choice because the in-
that is characterized by satisfactory boiling point, vestment is relatively low and the reaction efficiency
good solubility, volatilization, and stability and is is comparatively high.
nontoxic. It is widely used as a solvent in paint, dye, There are two ways to produce MEK via dehy-
pharmaceutical, and refining industries. MEK is also drogenation of butyl alcohol: gas dehydrogenation and
as an important raw material for organic chemical in- liquid dehydrogenation. Gas dehydrogenation is widely
dustries and is used for the production of MEK perox- used in the industry because it involves a simpler proc-
ide and oxime, as an intermediate in the perfumery in- ess flow sheet and the investment is low. The key to
dustry, as an antioxidant, and for catalyst production[1,2]. technical development is the improvisation of the cata-
With its expanding application in various industries, lyst activity, selectivity, and operation cycle[48].
the producing capacity of MEK has shown an average In China, a large amount of n-butylene exists in
annual increase of 5%10% in many countries. Before liquefied gas and is mostly used as fuel. MEK has to
2001, there were only two MEK-production sites in be imported from other countries. From the point of
China, both licensed by Deutsche Texaco Manufacture view of resource conservation, the C4 resource will
Technique, and the annual output was only about certainly be used for producing MEK from n-butylene
20kta 1, which was far from satisfying the demand of

in the near future in China.
the domestic market and therefore at least 100kta 1

After a thorough investigation of the entire tech-
MEK had to be imported. In 2004, the capacity was nology of n-butylene direct hydration and dehydroge-
increased to 185kta 1, and the output was 110kta 1.

nation, Fushun Research Institute of Petroleum &
By 2007, it is predicted that the demand for MEK Petrochemicals (FRIPP) developed high-performance,
would be 230240kta 1 in China[3].

heat-resistant catalysts for the hydration of butylene
Currently, MEK is commercially produced using and the FDH-type specialty catalyst for the dehydro-
the two-step n-butylene technique: hydrating butylene genation of SBA. On the basis of these, the operating
to produce secondary butyl alcohol (SBA) and then conditions, such as reaction process parameters, dy-
dehydrogenating the SBA. Based on different cata- namics, and thermal stability, were optimized. Under
lysts, there were three main processes: vitriol indirect the optimized operating conditions and with the use of
hydration, resin direct hydration, and motley acid di- specialty catalysts, the butylene per pass conversion
rect hydration. was more than 8%, the selectivity of SBA was more
Because of huge energy consumption; high cost than 98%, the conversion of SBA was greater than
of investment; serious equipment cauterization; and 85%, and the selectivity of MEK was more than 96%;
complicated treatment procedures for the exhaust gas, all these techniques have been patented.
wastewater, and waste residue, the use of vitriol indi- Compared with the other licensers, FRIPPs
rect hydration process declined gradually. In the case technology is characterized by the following features:
of the motley acid hydration process, the investment is Hydration reaction adopts low LHSV and high
too high and the operating condition is too rigorous; water/butylenes ratio; therefore, less amount of
therefore, this process is not the best choice. On the 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 677

sumption is low; Figure 1 shows the procedure for the commercial


To recycle water, azeotropic distillation col- production of MEK from a 2L pilot plant reactor, the
capacity was 20kta 1, which was scaled up; the

umn is used in this process;
The conversion is improved by lowering the structure and dimension are as follows.
SBA concentration in recycled water through 2.1.1 Hydration reactor
the SBA-recovery technique; Figure 2 shows the diagram of hydration reactor,
Pollution is well controlled by lowering the which is a cylinder. The feed hydrocarbon was
concentration of organics in the discharged pumped from the bottom of the hydration reactor, this
water through the recycling of water. in turn moved upward through the column beds, re-
acted with the deionized water, and, finally, the end
2 EXPERIMENTAL product was discharged from the top of the reactor.
2.1 Test method and process flow The four sections are similar in design: each is
From the flow chart shown in Fig.1, it can be 3m high and 11.25m3 of resin catalyst can be loaded;
seen that n-butylene and deionized water were therefore, the total amount of catalyst loaded is 45m3.
pumped into the bottom of hydration reactor, where Each section has a catalyst-loading inlet and a
the hydration reaction took place. The SBA thus pro- discharge outlet, a sprayer for water-in, and a derivate
duced was discharged from the top of the reactor into pipe. There is a gas distributor for feed gas under each
the phase-separator. The SBA and unconverted hy- catalyst bed, which consists of a gas flier trough and a
drocarbons were separated from the water to form the bubble cap tray, the feed sprays through the slots of
upper layer, which then entered the distillation column, the bubble cap tray. The sprayer for water-in is located
where unconverted hydrocarbon was separated from on the catalyst bed. The feed hydrocarbon was
the SBA. The unconverted hydrocarbon was at the top pumped from the bottom of the hydration reactor.
of the column, whereas the SBA was at the bottom of There is a space of 1.1m height above each sec-
the column. The resultant SBA then entered the inter- tion to allow thermal expansion, and each bed has a
mittent distillation column, wherein it was space of 0.8m height for separating the fogs.
separatedlight distillates were at the top of the The operating conditions of the hydration reactor
column, heavy distillates were at the bottom, and the were as follows: reaction temperature, 135175;
reaction pressure, 8.0MPa; LHSV, 1.0h 1 1.2h 1;

SBA product was in the middle. The SBA product then
entered into a vaporizer to boil-off and was then intro- mass flow rate of water and butane, 2.02.5; and
online time, 8000ha 1.

duced from the top of the vaporizer into the dehydro-
genation reactor. The resultant MEK, from the bottom 2.1.2 Dehydrogenation reactor
of the dehydrogenation reactor, was cooled inside a Reaction pressure: 0.6MPa. Diameter: 1000mm.
condenser and then moved into a phase-separator, The catalyst loaded in the tubes and heat-conduction
wherein the hydrogen was separated at the top and the oil of 260320 runs in shells. The volume of
MEK product was obtained at the bottom. catalyst in each reactor was 700L. There were two
The wastewater containing alcohols discharged reactors and the structure is as given below. Tubes are
from the bottom of the phase-separator entered the arranged in rows: 25mm2.5mm, the length is
flash tower where it was distilled. The azeotropic SBA 3000mm, total number of tubes is 740, which were
mixture from the top of the flash tower entered the arranged as a normal triangle, and the space between
intermittent distillation column. The water discharged each tubes is 32mm.
from the bottom of the flash tower was treated by both The operating conditions of the dehydrogenation
anion exchange column and ion exchange column, and reactor are: Reaction pressure in inlet, 0.2MPa; re-
was recycled[9,10]. action 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

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: 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

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 (1) Thermal stability
20;subsequently, bromine was slowly added and the In a glass tube, whose inner diameter was 10mm,
temperature was reduced to 0, After stirring for 10h, 3ml of catalyst and 6ml of water were added; the glass
the bromination was completed, after which the poly- tube was sealed and placed in a high-pressure kettle.
mer resin was filtered, washed, and dried. At a temperature of 200, the samples were collected
(4) Sulfonation reaction every 8h. Then the exchange capacity of the resin
The polymer resin was swelled using dichloro- catalyst and the loss of sulfonic acid group were
ethane. Oleum (50%) was then added slowly with stir- measured according to HG2-885-76. The result is
ring, with the temperature maintained below 30. shown in Fig.3.
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
Figure 3 Static state satuation between the special catalyst
resin. The resin was heated to 150200 at 1MPa and reference
for 15d and washed using deionized water. B-24; DNW catalyst
Using the above-mentioned process, for every
batch in the commercial run, 5m3 of DNW speciality It can be seen from Fig.3 that the fraction of loss
resin high-temperature catalyst could be obtained, and of sulfo radical was lower than that of the overseas
the total amount of DNW catalyst needed for butane reference resin catalyst over 64h, which was tested at
hydration was 45m3. 200.
The characteristics of the DNW specialty catalyst (2) Hydration activity
are listed in Table 2. The reaction conditions were as follows: tem-
Compared with the traditional methods, the spe- perature, 150; pressure, 6.0MPa; water/butylene
molar ratio, 1.0; LHSV, 1.5h 1. The result for 120h is

cialty catalysts that were prepared using the special
method mentioned above had the following excellent shown in Fig.4.
characteristics: (1) high purity; (2) high stability; (3) From Fig.4 it was observed that for 120 h of con-
after the purification, the pore volume and specific tinuous running, the average conversion of DNW spe-
surface area were increased considerably. So the pore cialty resin catalyst was 5.42%, about 5.1% higher
size would centralize and distribute evenly; the life of 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)

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-
Figure 4 Reference catalyst and specialty catalyst of high perature of 150200.
temperature resistance for hydration reactions FDH catalyst prepared for SBA dehydrogenation
B-24; specialty catalyst for high temperature
has advantages, such as high strength, good selectivity,
2.4.3 Specialty FDH SBA dehydrogenation cata- long running time, low cost, and simple preparation.
lyst[1214] The characteristics of the catalyst are listed in Table 3.
(1) Preparation of matrix catalyst 2.4.4 Comparison of the specialty FDH dehydroge-
Aluminum nitrate (220kg) and zinc nitrate (254kg) nation catalyst and other catalysts
with copper nitrate (338kg) as solution were mixed in To show the better capability of the FDH catalyst,
3m3 of deionized water. Sodium carbonate (498kg) and author compared the results of specialty FDH catalyst
deionized water (3m3) were mixed as precipitator. on the 200ml secondary butanol test equipment in
A little deionized water was added into a 10m3 miniature with those of the D01 catalyst, which was
reaction tank to submerge the stirrer and heated to produced by JGC in Japan, under the following condi-
85, the water solution and precipitator were sepa- tions: temperature, 260; pressure, 0.2MPa; LHSV,
0.34h 1. The results are listed in Table 4. From Table

rately heated to 85 and then added to the tank in
parallel-flow, slowly with strong stirring for about 4 it can be found that of all the catalysts used world-
1.5h; the temperature was kept at 85 and pH was wide, the FDH catalyst showed maximum reactivity.
adjusted to 7.08.0 by controlling relative flow-rate
of water solution and precipitator and then sodium 3 RESULTS AND DISCUSSION
hydroxide solution was added to adjust the pH to 9.5. 3.1 Optimization of the n-butylene hydration proc-
The precipitate was washed using deionized water ess parameters
after aging for 0.5h, it was then dried until the water 3.1.1 Influence of reaction temperature on conver-
content was reduced to 0.5%, uniformly mixed with sion
Under the conditions of 8.0MPa pressure, 0.34h 1

25kg graphite, and then it was made into
5mm5mm pellets and calcined at 380 for 6h; LHSV, and water/butylene molar ratio of 10, the in-
305kg of matrix catalyst was thus obtained and it fluence of reaction temperature on conversion was
contained 46.0% (by mass) copper oxide, 18.5% (by investigated in the commercial unit. The results are
mass) alumina oxide, and 35.5% (by mass) zinc oxide. shown in Fig.5.
(2) Alkali metals loading From Fig.5 it can be seen that reaction tempera-
A total of 150kg of the matrix catalyst was added ture had a considerable influence on the conversion.
into a 500L vitreous enamel tank, which had a wa- The higher the temperature, the greater the speed
ter-cooling system, 300L of niter (1.5molL1) was of reaction until 150. Under the above-mentioned

Table 3 Characteristics of FDH dehydrogenation catalyst


Item FDH D01
appearance pellets pellets
particle size, mm 55 66
component CuO-ZnO-Al2O3 CuO-ZnO
pore volume, mlg1 0.150.20 0.12
2 1
specific surface area, m g 58.00 36.2 (average)
1
bulk density, gml 1.48 1.75
average pore diameter, nm 12.00 13.60
radial crashing strength, MPa 14.00 10.00 (average)
D01 was produced by Deraito in Japan.
Table 4 Comparison of reactivity of different catalysts
Catalyst Conversion of alcohol,% Selectivity of MEK, % Selectivity of C8 ketone, %
FDH 81.90 97.40 2.50
D01 76.80 96.80 2.70

October, 2006
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.

Figure 8 Influence of LHSV on conversion


Figure 6 Curve of concentration versus conversion concentration of butylenc: 99%; 77%

Table 5 Influence of reaction pressure on conversion


Pressure, Temperature, Volume velocity of nC4, Average conversion of butylenes,
Water/butylene mol ratio
h 1

MPa % (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

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- 3.2.2 Influence of pressure


ter/butane molar ratio and LHSV had considerable The overall reaction is a gas phase reaction in-
influence on conversion and that the conversion of a creased with the number of molecules, so while the
related curve became higher as the molar ratio of wa- reaction pressure increased, the conversion of SBA
ter/butane increased. So, with a fixed water/butanes decreased. The equilibrium conversion of SBA dehy-
molar ratio (or fixed total water amount), total conver- drogenation could be expressed as given below:
sion improvement depended on stepping seed. 1
K p 2
X =
3.2 Optimization of operating parameters for P + Kp
SBA dehydrogenation
3.2.1 Influence of temperature 2790
lg K p = + 1.510lg T + 1.865
Under normal pressure, LHSV of 4.0h 1 for SBA,

T
and temperature of 230290, the influence of tem- where: X, conversion of SBA; P, reaction pressure,
perature on SBA conversion and MEK selectivity was MPa; Kp, equilibrium constant of SBA dehydrogena-
tested with FDH catalyst. The results are shown in Fig.9. tion, MPa; T, reaction temperature, K.
The relationship of reaction pressure and equilib-
rium conversion is shown in Fig.11.

Figure 9 Influence of reaction temperature on conversion


selectivity of MEK; conversion of SBA;
selectivity of C8 ketone Figure 11 Relation of equilibrium conversion and
pressure
From Fig.9 it can be observed that there was an 230; 260
obvious increase in the conversion of SBA as the re-
Under the condition of temperature of 260 , the
action temperature increased. The conversion of SBA
results of different reaction pressure are listed in Table 6.
was above 80% while the temperature was over 250,
From Table 6 it can be observed that the conver-
and the selectivity of MEK slightly increased, all more
sion of SBA and the selectivity of MEK decreased
than 95%, and the selectivity of C8 ketone declined.
with increase in pressure because of the increasing
The by-reaction of SBA dehydration increased when
rate of the MEK condensation reaction. But for the
the reaction temperature continued to rise.
pressure drop and industrial equipment controlling,
From Fig.10 it can be observed that SBA could
actual pressure must be about 0.2MPa. Under this
dehydrate and crack easily when the reaction tem-
pressure, the conversion of SBA could reach more
perature rose, and carbon deposited on catalyst be-
than 80% under conditions of temperature of 260
came more concentrated. So, lower reaction tempera-
and LHSV of 4.0h 1.

ture was good for the long-period catalyst operation


3.2.3 Influence of LHSV
and for maintaining adequate SBA conversion.
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-
Figure 10 Variety of butylenes and water to reaction sion of SBA was reduced and the circulation of SBA
temperature
Table 6 Influence of reaction pressure on conversion
1
Temperature, LHSV, h Pressure, MPa Conversion of SBA, % Selectivity of MEK, % Selectivity of C8 ketone, %
260 4.00 0.10 85.33 97.65 2.41
260 4.00 0.20 81.81 96.25 3.24
260 4.00 0.50 65.34 93.23 6.22

October, 2006
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.

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-
tivity all met the design targets, and MEK product REFERENCES
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results and reference technique data are shown in Ta- methyl ethyl ketone, Fine and Specialty Chemicals,
ble 7. 12(18), 2225(2004). (in Chinese)
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status of methyl ethyl ketone, Journal of Henan Chemi-
that, using the technology developed FRIPP, though
cal Industry, 11(1), 5155(2003). (in Chinese)
the volume of catalyst is slightly increased, the initial 3 Qi, J., Gao, N., Market analysis of methyl ethyl ketone,
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684 Chinese J. Ch. E. (Vol. 14, No.5)

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October, 2006