Chinese J . Chem. Eng.

, 14(5) 67&684

(2006)

Development and Commercial Application of Methyl-ethyl-ketone Production Technology
LIU Zhenhua(34 #Zq)a,b, HUO Wenzhou(%&H )b9*, MA Hao( 9
Dalian University of Technology, Dalian 116024, China bFushun Research Institute of Petroleum & Petrochemicals, Fushun 113001, China

and QIAO Kai($ $A)b

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

1 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"**'. 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 Techni ue, and the annual output was only about 20kt.a', which was far from satisfying the demand of the domestic market and therefore at least 100kt.a-' MEK had to be imported. In 2004, the capacity was increased to 185kt.a-', and the output was llOkt.a-'. By 2007, it is predicted that the demand for MEK would be 230-240kt.a-' in ChinaI3'. 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 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, FRIPP's technology is characterized by the following features: 0 Hydration reaction adopts low LHSV and high waterhutylenes 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.corn.cn

azeotropic distillation column is used in this process. reaction temperature. The resultant MEK.a-'. reaction pressure. finally. and a derivate pipe. Diameter: @lOOOmm. 1. The SBA thus produced was discharged from the top of the reactor into the phase-separator. The conversion is improved by lowering the SBA concentration in recycled water through the SBA-recovery technique. Ch. The operating conditions of the dehydrogenation reactor are: Reaction pressure in inlet. The unconverted hydrocarbon was at the top of the column.2 Dehydrogenation reactor Reaction pressure: 0. which then entered the distillation column.Development and Commercial Application of MEK Production Technology 677 sumption is low.1 Hydration reactor Figure 2 shows the diagram of hydration reactor. Tubes are arranged in rows: @5mmX2. The volume of catalyst in each reactor was 700L. which were arranged as a normal triangle. total number of tubes is 740. 6-anion column. 3-distillation column. 2-hase-separator.2h-I. The water discharged from the bottom of the flash tower was treated by both anion exchan e column and ion exchange column.101 . 8. which consists of a gas flier trough and a bubble cap tray. To recycle water.25m3of resin catalyst can be loaded. The catalyst loaded in the tubes and heat-conduction oil of 26OoC-32O0C runs in shells. wherein it was separated-light distillates were at the top of the column. The feed hydrocarbon was pumped from the bottom of the hydration reactor. LHSV of SBA. the feed sprays through the slots of the bubble cap tray. 11-phase-separator Chinese J. the structure and dimension are as follows. Each section has a catalyst-loading inlet and a discharge outlet. whereas the SBA was at the bottom of the column. the end product was discharged from the top of the reactor.1.8. There were two reactors and the structure is as given below. 14(5) 676 (2006) . height for separating the fogs. There is a space of l . this in turn moved upward through the column beds.1. t tail hydrocarbons t light distillate hydrogen hydrocarbon de-ionized water MEK water heavy distillate Figure 1 Process flow chart of n-butylene hydration and dehydrogenation 1-hydration reactor.2MPa.6MPa. wherein the hydrogen was separated at the top and the MEK product was obtained at the bottom. The sprayer for water-in is located on the catalyst bed. The wastewater containing alcohols discharged from the bottom of the phase-separator entered the flash tower where it was distilled.0-2. There is a gas distributor for feed gas under each catalyst bed. and. 3 crude Figure 1 shows the procedure for the commercial production of MEK from a 2L pilot plant reactor. from the bottom of the dehydrogenation reactor. and the SBA product was in the middle. The four sections are similar in design: each is 3m high and 11. the capacity was 20kt. and was recycled8. 60. and the space between each tubes is 32mm. it can be seen that n-butylene and deionized water were pumped into the bottom of hydration reactor.5. LHSV. which was scaled up. 2 EXPERIMENTAL 2. 8000h-a-'. Pollution is well controlled by lowering the concentration of organics in the discharged water through the recycling of water. 135"C--175"C . 2. where the hydration reaction took place. therefore. and each bed has a space of 0.0h-I-1. The feed hydrocarbon was pumped from the bottom of the hydration reactor. l m height above each section to allow thermal expansion. where unconverted hydrocarbon was separated from the SBA.1. 7-flash tower. 4intermittent distillation column. 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 azeotropic SBA mixture from the top of the flash tower entered the intermittent distillation column. 9-dehydrogenation reactor. 8-vaporization. 5-ion column. The operating conditions of the hydration reactor were as follows: reaction temperature.5mm. The SBA and unconverted hydrocarbons were separated from the water to form the upper layer.1 Test method and process flow From the flow chart shown in Fig. 25O"C-28O0C. and online time. the total amount of catalyst loaded is 45m3. which is a cylinder. E. reacted with the deionized water. 1-condenser. a sprayer for water-in. was cooled inside a condenser and then moved into a phase-separator. heavy distillates were at the bottom. the length is 3000mm.0MPa. mass flow rate of water and butane. 2. 2. The resultant SBA then entered the intermittent distillation column.

From the thermodynamic point of view. H H I I oil phase was added within 2h. and sieved.15% (by mass) and methylene blue 0. CH. the scheduled online time of catalyst.2 SBA dehydrogenation The reaction equation is: I CH3CHOHCH2CH3=. Q=36. -CH. NOS) 4 water hat Through the above-mentioned reversible reactions. CH.C'H .C'H-CH.22 The composition of butylene feed (%. + H. with the number of molecules increasing. + H+= I (2) Physics structure stabilization H The polymer resin was swelled for 3h using dichloroethane. 14. . 1 year.5% (by mass) divinylbenzene were mixed together. + C+H-CH. The water phase was heated to 60°C with stirring. 6-8 weeks. Q=38.1 Specialty resin catalyst of high temperature resistancefor butylenes hydration'"] (1) Polymerization reaction A total of 64% (by mass) styrene and 7. (Vol.678 Chinese J.Oh-'. 100°C in 10h.H 2 CH3CH2C(CH3)CHCOCH2CH3 H20 The process is an endothermic reaction.85 trans-Butylene-2 46.5W-rnol-'.2 Reaction routes 2.09 October.CH2 .3 Feed The composition of butylene feed is listed in Table 1.67 iso-Butylene 0.76 n-Butane 19. The reaction equilibrium constant K .5: 1.2.5% (by mass) 56# paraffin wax and 1% (by mass) ~C~H~OH=CH~CH~(CH~)CHOCH(CH~)CH~CH~+HZO benezoperoxide were added to form the oil phase.CH3COCH2CH3+H2 +Q Q=. E.C'H .CH.40 .5 lOlgT + 1.. .CH2-CH The volume ratio of water phase to oil phase was CH3 + H' +CH. and unstable components were removed CH3-CH2. .H20 2CH3COCH2CH3 -I.-CC-CH3 + H+ + was adjusted to control the size and equality of oil drops. and then the stirring CH.CH. - Table 1 Propane 0. which were then added to deionized water lenes in the presence of H+to the same carbonium ions: 99. dried.2. 4. low temperature and high pressure will benefit the reaction. Then. 245-833pm polymer resin was H obtained after the oil drops were washed with hot waI ter.-C-C-CH. Q=43kJ.6W-mol-' for tr~ns-butylene'~].mol-' for cis-butylene[21.01% (by lyst with strong acid is based on the conversion of butymass). The main by-reactions are: C~H~OH+~-C~HS= The by-reactions are: 2CH3CHOHCH2CH3= CH~CH~CH(CH~)O(CH~)CHCHZCH-~ 4.5 IkJ~mol-'. is: Ig K .O 4 OH CH. = -2.1 n-butylene hydration reaction The general reaction equation of butylene hydration is: ~-C~HS+H+=CH~CH(OH)CH~CH~+Q This is an exothermic reaction: for n. + 2. 2006 Propylene 0. and then CH3CH2(CH3)CHOCH(CH3)CH2CH3+H20 27.790 T + 1. the carbonium ion can be reverted to any kind of butylenes or to SBA alternatively: CH.CH .CH. WE) Water phase was obtained using polythene alcoThe reaction mechanism of ion exchange resin catahol 0. Ch. by mass) cis-Butylene-2 31. Solidification of oil drops occurred at 95CH3-CH.54 n-Butylene-1 0. and the period for catalyst regeneration.4 Catalyst preparation 2.4. 2.84% (by mass). .865 Figure 2 Diagram of a hydration reactor 4.butylene"].CH. + H' 2. 2.

I 20 40 time.bromine was slowly added and the temperature was reduced to 0°C .42%. h 60 80 Figure 3 Static state satuation between the special catalyst and reference B-24. E. 2. mo1. with the temperature maintained below 30°C. (2) Hydration activity The reaction conditions were as follows: temperature.0MPa and 160°C for 15h. Table 2 The characteristics of hydration catalysts Item appearance type ion status water content. the samples were collected every 8h.g-' DNW brown particle strong acid H+type 50. the catalytic activity of the DNW specialty catalyst was compared with that of the B-24 catalyst.g-l exchange capacity. mm wet specific volume. (3) Bromination The polymer resin was initially swelled using dichloroethane. 1. Then the exchange capacity of the resin catalyst and the loss of sulfonic acid group were measured according to HG2-885-76.3. At a temperature of 200"C.Development and Commercial Application of MEK Production Technology 679 using series derivatives. the life of catalysts was considerably extended. the bromination was completed. (3) after the purification. the pore volume and specific surface area were increased considerably.4. The volume of the solvent was about 3 times that of the polymer resin and was maintained at 4.L-' specific surface area. From Fig. pressure. and dried. with the temperature maintained below 20°C. Chinese J. Compared with the traditional methods. After stirring for 10h.1% higher than that of the reference commercial catalyst. The result is shown in Fig. Using the above-mentioned process. washed. (1) Thermal stability In a glass tube. The characteristics of the DNW specialty catalyst are listed in Table 2. The stabilization was completed after the polymer resin was purified by ethanol for 15h. which was tested at 200°C. LHSV. hydrochloric acid.20 B-24'O bottle-green particle strong acid H+ type 57. and the total amount of DNW catalyst needed for butane hydration was 45m3. Ch.3 that the fraction of loss of sulfo radical was lower than that of the overseas reference resin catalyst over 64h. deionized water until the resin water was neutral. for every batch in the commercial run.2 Comparison o f specialty catalyst and overseas commercial catalyst To indicate the predominant capability of the specialty catalyst. 1. % particle size. after which the polymer resin was filtered. about 5. Stirring was then continued for 12h at 50°C. The resin was heated to 150-200°C at lMPa for 15d and washed using deionized water.09 0.0MPa. whose inner diameter was lOrnm. the average conversion of DNW specialty resin catalyst was 5. 6.95 1. W DNW catalyst + It can be seen from Fig.90 1.subsequently.30 10.4cF1. m2. and dried.00 0.00-20. and the loss of sulfo radicals was decreased.5h-'. Oleum (50%) was then added slowly with stirring. waterhutylene molar ratio. (2) high stability. The brominated and strongly acidic cation exchange resin was obtained after washing sequentially with NaCl solution.20 0.3 1 @ The catalyst was produced by Rohm & Hass in the USA. ( 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.40-1.4. 5m3 of DNW speciality resin high-temperature catalyst could be obtained. So the pore size would centralize and distribute evenly. and then ferric chloride 1% was added with stirring.0. the specialty catalysts that were prepared using the special method mentioned above had the following excellent characteristics: (1) high purity. The result for 120h is shown in Fig. m1. 150°C. s 35.00 0. 14(5) 676 (2006) . washed.00 0. 3ml of catalyst and 6ml of water were added. (4) Sulfonation reaction The polymer resin was swelled using dichloroethane. the glass tube was sealed and placed in a high-pressure kettle.4 it was observed that for 120 h of continuous running.

80 Selectivitv of Ca ketone. 260°C. Before being used.90 76. catalyst should be activated by nitrogenhydrogen mixed gas or SBA under temperature of 150-200 "C.00 1. then dried. the water solution and precipitator were separately heated to 8 5 T and then added to the tank in parallel-flow.15--0. % 97. 35. and 35. A little deionized water was added into a 10m3 reaction tank to submerge the stirrer and heated to 85"C. which contained 45.L-') was P added and heated for 3h with liquid cycling. and then it was made into @mmX 5mm pellets and calcined at 380°C for 6h.34h-' LHSV. 14. under the following conditions: temperature.5%. author compared the results of specialty FDH catalyst on the 200ml secondary butanol test equipment in miniature with those of the DO1 catalyst. and simple preparation. long running time. such as high strength. No.14 (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.4.' specific surface area.5mol. Under the above-mentioned Table 3 Characteristicsof FDH dehydrogenationcatalyst Item appearance particle size. g m .' average pore diameter. The precipitate was washed using deionized water after aging for 0.40 96. m m component pore volume.5 it can be seen that reaction temperature had a considerable influence on the conversion.5h. 18. The characteristics of the catalyst are listed in Table 3.4 Comparison of the specialty FDH dehydrogenation catalyst and other catalysts To show the better capability of the FDH catalyst.g-' bulk density.1. and waterhutylene molar ratio of 10.1% zinc oxide.4. 300L of niter (1. d . FDH catalyst prepared for SBA dehydrogenation has advantages.12 36. Sodium carbonate (498kg) and deionized water (3m3) were mixed as precipitator.2% kalium oxide. Table 4 Comparison of reactivity of different catalysts Catalyst FDH D O1 Conversion of alcohol. uniformly mixed w 25kg graphite.680 Chinese J.4% copper oxide.2MPa.00 (average) 0 DO1 was produced by Deraito in Japan.3 S ecialty FDH SBA dehydrogenation catalyst~ 12. g . low cost. which was produced by JGC in Japan.5.80 Selectivitv of MEK. h Figure 4 Reference catalyst and specialty catalyst of high temperature resistance for hydration reactions + B-24.75 13.0 by controlling relative flow-rate of water solution and precipitator and then sodium hydroxide solution was added to adjust the pH to 9.5) " running time. pressure. the temperature was kept at 85°C and pH was adjusted to 7. MPa FDH pellets @5X5 D O 1''I pellets ~56x6 CuO-ZnO 0.70 October. % 2.3% alumina. which had a water-cooling system. From Table 4 it can be found that of all the catalysts used worldwide.2 (average) 1. the greater the speed of reaction until 150°C.OMPa pressure. FDH catalyst for SBA dehydrogenation was thus obtained. it was then dried until the water i t h content was reduced to 0.34h-'. 3 RESULTS AND DISCUSSION 3. m2. 0.5h.W8. Ch. (2) Alkali metals loading A total of 150kg of the matrix catalyst was added into a 500L vitreous enamel tank.5% (by mass) zinc oxide.50 2. 0.1 Optimization of the n-butylene hydration process parameters 3.5. 305kg of matrix catalyst was thus obtained and it contained 46. The higher the temperature. The results are shown in Fig. From Fig. and calcinated at 360°C for 6h. slowly with strong stirring for about 1. E.00 10.% 8 1. (Vol.5% (by mass) alumina oxide. nm radial crashing strength. 0.0% (by mass) copper oxide.48 12. the influence of reaction temperature on conversion was investigated in the commercial unit. and 1.00 2 14. 2. The results are listed in Table 4. the FDH catalyst showed maximum reactivity. good selectivity.60 Cu0-Zn0-AI2O3 0. specialty catalyst for high temperature 2. LHSV.1 Influence o f reaction temperature on conversion Under the conditions of 8.20 58. 2006 . 18.

Ch. It was found that the reaction pressure could considerably affect the hydration of butylenes. The results are shown in Fig. cis-butylene-2. 1 . n-butylene existed under the condition of supercritical pressure. The results are shown in Table 5.0MPa.LHSV. E. 3 . % (mol) 10 0. So. 1 . the influence of reaction pressure on conversion was observed. The results are shown in Fig. temperature was 15OoC. "C 150 150 150 Table 5 Influence of reaction pressure on conversion Volume velocity of nC4. and 3. The partial pressure of n-butylenes decreased when the impurities increased.2 0. the larger the driving force necessary to drive n-butylene from the organic phase to the water phase.4 0. therefore. 3 Influence of feed butylene Concentration on conversion Under the conditions of 8. 0. 1 2 1 2 waterhutylene. and trans-butylenes. such as propane. the saturated vapor pressure of water.918MPa.7. Figure 7 Influence of waterhutylenes on conversion LHSV 0. When temperature was 15072. The results are shown in Fig.00 Temperature.the influence of the waterhutylene molar ratio on conversion was investigated. and 10 waterhutylene molar ratio.0 The influence of LHSV on conversion was investigated under the following conditions: pressure.8 1.6. A LHSV 0. 3 .0MPa.0MPa pressure.8.6 LHSV. "C 160 170 Figure 5 Curve of temperature to conversion 3 . and the concentration of butylenes was 88%. it was observed that the conversion of butylenes was linear with the feed butylenes concentration. 2 Influence of reaction pressure on conversion Under the condition of butylene concentration of 88%. 2' 50 2 0 0. 3. normally.80 10.2 60 70 80 90 100 110 concentration. there were impurities. n-butane. Apart from n-.OMPa.34. respectively.2.5. 150°C.0 1. the conversion of the reaction increased with the increase of the concentration of n-butylenes. * LHSV 1. % (volume) I I I I I I Figure 6 Curve of concentration versus conversion Figure 8 Influence of LHSV on conversion concentration of butylenc: A 99%.00 6.10 10. The higher the butylenes concentration in feed. cis-. the concentration of SBA in water solution is close to the equilibrium concentration. 1. the reaction temperature cannot exceed 150°C.Development and Commercial Application of MEK Production Technology 681 reaction condition.435MPa. 14(5) 676 (2006) .00 Chinese J.6. which resulted in high n-butylene concentration on catalyst surface and made the reactions easier.34 0. '&I I From Fig. h-' 0. in the raw material. propylene. W 77% Pressure.5.34 9. 150°C temperature. and waterhutylene molar ratio. and iso-butylenes. the by-reaction occurs easily. temperature. 8. I I 110 120 130 140 150 temperature. 4 Influence of LHSV on conversion When pressure was 8.0MPa.34h. Waterhutylene mol ratio h-' Average conversion of butylenes. Therefore. 1 . the impetus of the reaction was reduced.34 0.40 10 10 8.712MPa. The effect of increase of pressure on the solubility of n-butylene seemed negligible. and trans-butylene-2 was 4. if the temperature is increased. mol + LHSV 0. MPa 4. the influence of feed butylene concentration on conversion was investigated. When the pressure reached S. The total saturated vapor pressure was about 4.

s U 40 + 0 0. so while the reaction pressure increased. The conversion of SBA was above 80% while the temperature was over 250eC. (Vol. the results of different reaction pressure are listed in Table 6. the conversion of SBA was reduced and the circulation of SBA Table 6 Influence of reaction pressure on conversion Temperature. MPa From Fig.2.00 4.2 Influence of pressure The overall reaction is a gas phase reaction increased with the number of molecules. 12.9 1. and temperature of 23W290°C.6 0.65 96. MPa.1 Influence of temperature Under normal pressure.9 it can be observed that there was an obvious increase in the conversion of SBA as the reaction temperature increased. all more than 95%.9. The relationship of reaction pressure and equilibrium conversion is shown in Fig. reaction temperature.2 0. 11. The equilibrium conversion of SBA dehydrogenation could be expressed as given below: 1 3. Figure 12 indicates that the conversion of SBA decreased with the increase of LHSV. reaction pressure.5101gT + 1.The results are shown in Fig. Under this pressure. reaction temperature. Because the MEK condensation reaction slowed down with the decrease in residence time. and carbon deposited on catalyst became more concentrated.23 Selectivity of CBketone. MPa."C 260 260 260 LHSV. So.4 0.50 Conversion of SBA.34 Selectivity of MEK. LHSV of 4.33 81. E. equilibrium constant of SBA dehydrogenation. actual pressure must be about 0. the conversion of SBA decreased. If the LHSV was too high.0h-I. Ch.2. lower reaction temperature was good for the long-period catalyst operation and for maintaining adequate SBA conversion. A conversion of SBA. % 97. the quantity of byproduct C S ketone was reduced. =--2790 + 1. Kp. 'C Figure 10 Variety of butylenes and water to reaction temperature Under the condition of temperature of 260 C .5 0.Oh-' for SBA.865 T where: X .10 0.20 0. conversion of SBA. whereas the MEK selectivity increased.2 Optimization of operating parameters for SBA dehydrogenation 3. with a fixed waterbutanes molar ratio (or fixed total water amount). 3. 14.3 0. "C Figure 9 Influence of reaction temperature on conversion W selectivity of MEK.4 1 3.25 93. % 85.8 0. h-' 4. 8 it can be observed that waterhutane molar ratio and LHSV had considerable influence on conversion and that the conversion of a related curve became higher as the molar ratio of waterbutane increased.7.1 0.2MPa. % 2. total conversion improvement depended on stepping seed. s e^ 100. So. The results are shown in Fig. selectivity of C8ketone . NOS) From Figs. W 260°C + 2 1 . 3. From Fig. lgK.3 Influence of LHSV Under normal pressure and temperature of 26OoC.00 4. the influence of LHSV on the conversion of FDH catalysts was investigated.22 October. the conversion of SBA could reach more than 80% under conditions of temperature of 260°C and LHSV of 4. -a Figure 11 Relation of equilibrium conversion and pressure 230'C. and the selectivity of C S ketone declined. 2006 . K.00 Pressure.2. The by-reaction of SBA dehydration increased when the reaction temperature continued to rise. But for the pressure drop and industrial equipment controlling.682 Chinese J.0 absolute pressure. MPa 0.7 0. the influence of temperature on SBA conversion and MEK selectivity was tested with FDH catalyst. 5s 0 * m 190 210 230 250 270 290 reaction temperature. T.10 it can be observed that SBA could dehydrate and crack easily when the reaction temperature rose. 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.24 6. and the selectivity of MEK slightly increased.81 65. P.

a-’ unit. so the energy consumption increased. REFERENCES Li. 12(18).0 >95. 3. Petrochemical Industry Technology. % 96. E.o 14. % 90. h-’ 4.0 n-butylene concentration. using the technology developed FRIPP. Y. The commercial results and reference technique data are shown in Table 7. and MEK product complied with the ASTM standard. 12 LHSV. % 96. H conversion of SBA + increased. MPa 0. And the operation cycle of the dehydrogenation catalyst was prolonged.. h >3500 0 The data was gained in Chinese industry by using technology from Germany.0 >80. the low recycle ratio of n-butylene resulted in the decreasing of recycling amount of n-butylene. MPa 6.0 98 80. “Market analysis of methyl ethyl ketone”. (in Chinese) Zhang. h-’ Figure 12 Influence of LHSV on conversion selectivity of MEK.0 catalyst life.1 LHSV. Fine and Specialty Chemicals. though the volume of catalyst is slightly increased. 22-25(2004). 51-55(2003).6 catalyst life.0 1008-1 344 ss 120. 14(5) 676 (2006) .. In general. “C 230-260 pressure.5 recycle ratio 10.0 22.0 SBA selectivity. At the same time. the both activity and selectivity of the two specialty catalysts were excellent. -a 683 FFWP Germanv techniaue” 97. % (by mass) temperature. 2 .0 catalyst volume.2 4. “Production technology and market analysis of methyl ethyl ketone”. m3 23..5 waterhutylenes ratio 1. J.gg m t $ 2 40 8% 0 . I .0-1. the conversion and selectivity all met the design targets.0 LHSV. the initial temperature of reaction was lower than before. the conversion of SBA was greater than 80%. The unit was started-up only by one trial. Journal of Henan Chemical Industry.0 1. 4 1 6 8 10 prolonged.7 MEK selectivity. % 98 n-butylene conversion. (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.L. Compared the data listed above. (in Chinese) Chinese J.X. 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. “Production technology and application status of methyl ethyl ketone”.Development and Commercial Application of MEK Production Technology Table 7 The commercial operating conditions of MEK unit Item hydration reaction 97. h 9000 dehydrogenation reaction temperature. The two specialty catalysts were both commercialized and successfully used in the commercial MEK unit. (2) On the basis of FRIPP technology.0 8 O O O 260 0.5 1. (in Chinese) Qi. Under the temperature of 260”C.0 160 6. h-’ 1. Gao.3 Commercial MEK technology The MEK production technology via n-butylene hydratiodSB A dehydrogenation was commercialized in a 20kt.a-’ MEK production unit was built and it operated well after first starting-up.0 SBA conversion.0-11. “C 135-175 pressure. Y. the whole set of production technology for n-butylene hydration and MEK production by dehydrogenation was successfully commercialized. it can be found that.. a 20kt. the appropriate LHSV of SBA was around 4. N. (3) Compared with those of the same kind of overseas catalysts. Ch.0 h-’. the conversion was enhanced and the life of catalyst was 4 CONCLUSIONS (1) Based on the laboratory and pilot plant studies in FRIPP. % 8. 6 1 64(2003).0 6. 10(3).3 single pass conversion of butylenes. and the MEK product met the ASTM standard. 11(l).0-1.

J. Wan.. Muter. 232(2). Ma...K. (in Chinese) Wu. 40( 12). C N Pat... Marcilio.... Ziyad. Y. 2089-2099(2005)..G. 37-5 l(2000). G.. Y. Zhang. “A process of seriate production low carbon alcohol”.. C.W. H.. Noble.G. Res. No.F.. 114(I). Wang. 57(l).S. C. Res. Bull. “Structural features of AgCaCdMg2(P04)3 and AgCd2Mg2(P04)3.S.T. P.. Farias. L. 1076385A(1993). Y. and their catalytic activity in butan-2-01 conversion”.L.. R. C N Pat. A.... Wang.. O.M.. 2006 . Wu. Su.R.S. Radiation Physics and Chemistry. 257-267(2005). “A process of aldehydes and ketones from alcohol by dehydrogenation”... (in Chinese) Driver. Q. Ziyad. J. J. Rouimi.. C N Pat. S. M. Wren.Y. 682-693(2005). Su.K. 9 5 10 11 12 13 14 6 7 8 October. 1210847(1999). 1289752(2001). Xu. F.S... “A process of low carbon alcohol by hydration directly from low carbon alkene” C N Pat. Mater. Cheikhi. Ch.M. C. Journal o f Membrane Science. N. Falconer. Zhu. M. J. Pantaleo.. N. 40(4).C. M. Zhu. Zhai. 1289638(2001). Z.N Pat.. B. “Direct synthesis of methyl isobutyl ketone in gas-phase reaction over palladium-loaded hydroxyapatite”..5) Perez-Lopez.. “Steady-state y-radiolysis of aqueous methyl ethyl ketone (2-butanone) under postulated nuclear reactor accident conditions”. M. Ma.. “The catalytic behavior of zinc oxide prepared from various precursors and by different methods”.. 1289748(2001).. J. Li. “A process of ketone from secondary alcohol by dehydrogenation”. “Separation of methyl ethyl ketone from water by pervaporation using a silicalite membrane”. Z. “A process of a Cu contained catalyst”. 1289753(2001). Journal o f Catalysis. (Vol. two new compounds with the alluaudite-type structure.C. Su.M. Kacimi.F.. “A process of cation exchange resin catalysts with high temperature resistance”.. J. C.. Liotta.. Ma. Hatert. M. J.. Deganello. Smetana.N Pat... GL.C.. 127-130( 1996). Bueno. 14. Glowa. S. Bull. Kacimi. G. J.D... G. E.684 4 Chinese J.

Sign up to vote on this title
UsefulNot useful